ARXPS analysis of a GaAs/GaInP heterointerface with application in III-V multijunction solar cells

In this contribution, angle-resolved X-ray photoelectron spectroscopy is used to explore the extension and nature of a GaAs/GaInP heterointerface. This bilayer structure constitutes a very common interface in a multilayered III-V solar cell. Our results show a wide indium penetration into the GaAs layer, while phosphorous diffusion is much less important. The physico-chemical nature of such interface and its depth could deleteriously impact the solar cell performance. Our results probe the formation of spurious phases which may profoundly affect the interface behavior.

Using array based techniques for noise source identification in cars

Una de las principales causas del ruido en nuestras ciudades es el tráfico rodado. El ruido generado por los vehículos no es sólo debido al motor, sino que existen diversas fuentes de ruido en los mismos, entre las que se puede destacar el ruido de rodadura. Para localizar las causas del ruido e identificar las principales fuentes del mismo se han utilizado en diversos estudios las técnicas de coherencia y las técnicas basadas en arrays. Sin embargo, en la bibliografía existente, no es habitual encontrar el uso de estas técnicas en el sector automovilístico. En esta tesis se parte de la premisa de la posibilidad de usar estas técnicas de medida en coches, para demostrar a la largo de la misma su factibilidad y su bondad para evaluar las fuentes de ruido en dos condiciones distintas: cuando el coche está parado y cuando está en movimiento. Como técnica de coherencia se elige la de Intensidad Selectiva, utilizándose la misma para evaluar la coherencia existente entre el ruido que llega a los oídos del conductor y la intensidad radiada por distintos puntos del motor. Para la localización de fuentes de ruido, las técnicas basadas en array son las que mejores resultados ofrecen. Statistically Optimized Near-field Acoustical Holography (SONAH) es la técnica elegida para la localización y caracterización de las fuentes de ruido en el motor a baja frecuencia. En cambio, Beamforming es la técnica seleccionada para el caso de media-alta frecuencia y para la evaluación de las fuentes de ruido cuando el coche se encuentra en movimiento. Las técnicas propuestas no sólo pueden utilizarse en medidas reales, sino que además proporcionan abundante información y frecen una gran versatilidad a la hora de caracterizar fuentes de ruido. ABSTRACT One of the most important noise causes in our cities is the traffic. The noise generated by the vehicles is not only due to the engine, but there are some other noise sources. Among them the tyre/road noise can be highlighted. Coherence and array based techniques have been used in some research to locate the noise causes and identify the main noise sources. Nevertheless, it is not usual in the literature to find the application of this kind of techniques in the car sector. This Thesis starts taking into account the possibility of using this kind of measurement techniques in cars, to demonstrate their feasability and their quality to evaluate the noise sources under two different conditions: when the car is stopped and when it is in movement. Selective Intensity was chosen as coherence technique, evaluating the coherence between the noise in the driver’s ears and the intensity radiated in different points of the engine. Array based techniques carry out the best results to noise source location. Statistically Optimized Near-field Acoustical Holography (SONAH) is the measurement technique chosen for noise source location and characterization in the engine at low frequency. On the other hand, Beamforming is the technique chosen in the case of medium-high frequency and to characterize the noise sources when the car is in movement. The proposed techniques not only can be used in actual measurements, but also provide a lot of information and are very versatile to noise source characterization.

On the production of N-2(+) ions at the N 1s edge of the nitrogen molecule

The N+2 ion yield of the N2 molecule has been measured at the N 1s → Rydberg excitations. It displays Fano-type line shapes due to interference between direct outer-valence photoionization and participator decay of the core-excited Rydberg states. The N+2 ion yield is compared with the total intensity of the outer-valence photoelectron lines obtained recently with electron spectroscopy (Kivimäki et al 2012 Phys. Rev. A 86 012516). The increasing difference between the two curves at the higher core-to-Rydberg excitations is most likely due to soft x-ray emission processes that are followed by autoionization. The results also suggest that resonant Auger decay from the core–valence doubly excited states contributes to the N+2 ion yield at the photon energies that are located on both sides of the N 1s ionization limit.

Propiedades de materiales mediante análisis de radiación aleatoria

Las técnicas de speckle tienen un gran interés científico e ingenieril, ya que son métodos de ejecución rápida y no destructiva, con base en el análisis de las fluctuaciones de intensidad de la radiación producida cuando la luz coherente de un haz láser es esparcida por un material dado. En este caso se produce un patrón aleatorio de interferencia y difracción donde la suma de las componentes desfasadas dará lugar a máximos y mínimos de intensidad en distintos puntos del espacio. Éste, pese a tratarse de un ruido nocivo en multitud de áreas tales como la transmisión de señales o la holografía, tiene importantes propiedades físicas que lo caracterizan y lo hacen útil como medio para analizar sistemas reales de muy diversa índole. En el presente estudio, se ha llevado a cabo un análisis polarimétrico de la radiación aleatoria esparcida por una serie de muestras metálicas y dieléctricas con el objetivo de establecer una base comparativa que nos permita poder distinguir unas de otras. Para este fin se han comparado los parámetros de polarización de Stokes, el grado de polarización de la luz, las distribuciones de intensidad y el tamaño medio del speckle registrado en los distintos patrones de intensidad. Además, se analizará la dependencia de la rugosidad en el grado de polarización de la luz para los distintos medios sometidos a estudio. Abstract Speckle techniques have a great scientific and engineering interest as they are methods of rapid and non-destructive execution, based on the analysis of the fluctuations of intensity of the radiation produced when coherent light of a laser beam is scattered by a material given. In this case, a random pattern of interference and diffraction occurs where the sum of phase shifted components will result in maximum or minimum of intensity at different points in space. This, despite being a harmful noise in many areas such as signal transmission or holography, has important physical properties that characterize it and make it useful as a means to analyze real systems of various kinds. In the present study, we have conducted a polarimetric analysis of the random radiation scattered by a series of metal and dielectric samples in order to establish a comparative basis to allow us to distinguish one from another. To this end we have compared, the stokes polarization parameters, the degree of polarization (DOP), the intensity distributions and the average size of the speckle registered in the different intensity patterns. Furthermore, dependence of roughness in the DOP of light for the different means under study will be analyzed.

Determination of a refractive index and an extinction coefficient of standard production of CVD-graphene

The refractive index and extinction coefficient of chemical vapour deposition grown graphene are determined by ellipsometry analysis. Graphene films were grown on copper substrates and transferred as both monolayers and bilayers onto SiO2/Si substrates by using standard manufacturing procedures. The chemical nature and thickness of residual debris formed after the transfer process were elucidated using photoelectron spectroscopy. The real layered structure so deduced has been used instead of the nominal one as the input in the ellipsometry analysis of monolayer and bilayer graphene, transferred onto both native and thermal silicon oxide. The effect of these contamination layers on the optical properties of the stacked structure is noticeable both in the visible and the ultraviolet spectral regions, thus masking the graphene optical response. Finally, the use of heat treatment under a nitrogen atmosphere of the graphene-based stacked structures, as a method to reduce the water content of the sample, and its effect on the optical response of both graphene and the residual debris layer are presented. The Lorentz-Drude model proposed for the optical response of graphene fits fairly well the experimental ellipsometric data for all the analysed graphene-based stacked structures.

Gravidade de Lovelock e a correspondência AdS/CFT

A correspondência AdS/CFT é uma notável ferramenta no estudo de teorias de gauge fortemente acopladas que podem ser mapeadas em uma descrição gravitacional dual fracamente acoplada. A correspondência é melhor entendida no limite em que ambos $N$ e $\\lambda$, o rank do grupo de gauge e o acoplamento de \'t Hooft da teoria de gauge, respectivamente, são infinitos. Levar em consideração interações com termos de curvatura de ordem superior nos permite considerar correções de $\\lambda$ finito. Por exemplo, a primeira correção de acoplamento finito para supergravidade tipo IIB surge como um termo de curvatura com forma esquemática $\\alpha\'^3 R^4$. Neste trabalho investigamos correções de curvatura no contexto da gravidade de Lovelock, que é um cenário simples para investigar tais correções pois as suas equações de movimento ainda são de segunda ordem em derivadas. Esse cenário também é particularmente interessante do ponto de vista da correspondência AdS/CFT devido a sua grande classe de soluções de buracos negros assintoticamente AdS. Consideramos um sistema de gravidade AdS-axion-dilaton em cinco dimensões com um termo de Gauss-Bonnet e encontramos uma solução das equações de movimento, o que corresponde a uma black brane exibindo uma anisotropia espacial, onde a fonte da anisotropia é um campo escalar linear em uma das coordenadas espaciais. Estudamos suas propriedades termodinâmicas e realizamos a renormalização holográfica usando o método de Hamilton-Jacobi. Finalmente, usamos a solução obtida como dual gravitacional de um plasma anisotrópico fortemente acoplado com duas cargas centrais independentes, $a eq c$. Calculamos vários observáveis relevantes para o estudo do plasma, a saber, a viscosidade de cisalhamento sobre densidade de entropia, a força de arrasto, o parâmetro de jet quenching, o potencial entre um par quark-antiquark e a taxa de produção de fótons.

Estimação de imagens acústicas com arranjos de microfones.

Nas últimas décadas, a poluição sonora tornou-se um grande problema para a sociedade. É por esta razão que a indústria tem aumentado seus esforços para reduzir a emissão de ruído. Para fazer isso, é importante localizar quais partes das fontes sonoras são as que emitem maior energia acústica. Conhecer os pontos de emissão é necessário para ter o controle das mesmas e assim poder reduzir o impacto acústico-ambiental. Técnicas como \"beamforming\" e \"Near-Field Acoustic Holography\" (NAH) permitem a obtenção de imagens acústicas. Essas imagens são obtidas usando um arranjo de microfones localizado a uma distância relativa de uma fonte emissora de ruído. Uma vez adquiridos os dados experimentais pode-se obter a localização e magnitude dos principais pontos de emissão de ruído. Do mesmo modo, ajudam a localizar fontes aeroacústicas e vibro acústicas porque são ferramentas de propósito geral. Usualmente, estes tipos de fontes trabalham em diferentes faixas de frequência de emissão. Recentemente, foi desenvolvida a transformada de Kronecker para arranjos de microfones, a qual fornece uma redução significativa do custo computacional quando aplicada a diversos métodos de reconstrução de imagens, desde que os microfones estejam distribuídos em um arranjo separável. Este trabalho de mestrado propõe realizar medições com sinais reais, usando diversos algoritmos desenvolvidos anteriormente em uma tese de doutorado, quanto à qualidade do resultado obtido e à complexidade computacional, e o desenvolvimento de alternativas para tratamento de dados quando alguns microfones do arranjo apresentarem defeito. Para reduzir o impacto de falhas em microfones e manter a condição de que o arranjo seja separável, foi desenvolvida uma alternativa para utilizar os algoritmos rápidos, eliminando-se apenas os microfones com defeito, de maneira que os resultados finais serão obtidos levando-se em conta todos os microfones do arranjo.

Metal and precursor effect during 1-heptyne selective hydrogenation using an activated carbon as support

Palladium, platinum, and ruthenium supported on activated carbon were used as catalysts for the selective hydrogenation of 1-heptyne, a terminal alkyne. All catalysts were characterized by temperature programmed reduction, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. TPR and XPS suggest that the metal in all catalysts is reduced after the pretreatment with H2 at 673 K. The TPR trace of the PdNRX catalyst shows that the support surface groups are greatly modified as a consequence of the use of HNO3 during the catalyst preparation. During the hydrogenation of 1-heptyne, both palladium catalysts were more active and selective than the platinum and ruthenium catalysts. The activity order of the catalysts is as follows: PdClRX > PdNRX > PtClRX ≫ RuClRX. This superior performance of PdClRX was attributed in part to the total occupancy of the d electronic levels of the Pd metal that is supposed to promote the rupture of the H2 bond during the hydrogenation reaction. The activity differences between PdClRX and PdNRX catalysts could be attributed to a better accessibility of the substrate to the active sites, as a consequence of steric and electronic effects of the superficial support groups. The order for the selectivity to 1-heptene is as follows: PdClRX = PdNRX > RuClRX > PtClRX, and it can be mainly attributed to thermodynamic effects.

Structure, gas-barrier properties and overall migration of poly(lactic acid) films coated with hydrogenated amorphous carbon layers

Hydrogenated amorphous carbon (a-C:H) films were grown on a poly(lactic acid) (PLA) substrate by means of a radiofrequency plasma-enhanced chemical vapour deposition (rf-PECVD) technique with different deposition times (5, 20 and 40 min). The main goal of this treatment was to increase the barrier properties of PLA, maintaining its original transparency and colour as well as controlling interactions with food simulants for packaging applications. Morphological, chemical, and mechanical properties of PLA/a-C:H systems were evaluated while permeability and overall migration tests were performed in order to determine the effect of the plasma treatment on the gas-barrier properties of PLA films and their application in food packaging. Morphological results suggested a good adhesion of the deposited layers onto the polymer surface and the samples treated for 5 and 20 min only slightly darkened the PLA film. X-ray photoelectron spectroscopy revealed that the structural properties of the carbon layer deposited onto the PLA film depend on the exposure time. PLA/a-C:H system treated for 5 min showed the highest barrier properties, while none of the studied samples exceeded the migration limit established by the current legislation, suggesting the suitability of these materials in packaging applications.

Surface modification of cellulose nanocrystals by grafting with poly(lactic acid)

The use of biopolymers obtained from renewable resources is currently growing and they have found unique applications as matrices and/or nanofillers in ‘green’ nanocomposites. Grafting of polymer chains to the surface of cellulose nanofillers was also studied to promote the dispersion of cellulose nanocrystals in hydrophobic polymer matrices. The aim of this study was to modify the surface of cellulose nanocrystals by grafting from L-lactide by ring-opening polymerization in order to improve the compatibility of nanocrystals and hydrophobic polymer matrices. The effectiveness of the grafting was evidenced by the long-term stability of a suspension of poly(lactic acid)-grafted cellulose nanocrystals in chloroform, by the presence of the carbonyl peak in modified samples determined by Fourier transform infrared spectroscopy and by the modification in C1s contributions observed by X-ray photoelectron spectroscopy. No modification in nanocrystal shape was observed in birefringence studies and transmission electron microscopy.

Preferential oxidation of CO in excess of H2 on Pt/CeO2–Nb2O5 catalysts

A series of CeO2–Nb2O5 mixed oxides with different Nb content, as well as the pure oxides, have been synthesized by co-precipitation with excess urea. These materials have been used as supports for platinum catalysts, with [Pt(NH3)4](NO3)2 as precursor. Both supports and catalysts have been characterized by several techniques: N2 physisorption at 77 K, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, UV–vis spectroscopy, scanning electron microscopy, transmission electron microscopy, temperature-programmed reduction and temperature-programmed desorption (CO and H2), and their catalytic behaviour has been determined in the PROX reaction, both with an ideal gas mixture (CO, O2 and H2) and in simulated reformate gas containing CO2 and H2O. Raman spectroscopy analysis has shown the likely substitution of some Ce4+ cations by Nb5+ to some extent in supports with low niobium contents. Moreover, the presence of Nb in the supports hinders their ability to adsorb CO and to oxidize it to CO2. However, an improvement of the catalytic activity for CO oxidation is obtained by adding Nb to the support, although the Pt/Nb2O5 catalyst shows very low activity. The best results are found with the Pt/0.7CeO2–0.3Nb2O5 catalyst, which shows a high CO conversion (85%) and a high yield (around 0.6) after a reduction treatment at 523 K. The effect of the presence of CO2 and H2O in the feed has also been determined.

Effect of the surface chemical groups of activated carbons on their surface adsorptivity to aromatic adsorbates based on π-π interactions

Three activated carbons with different surface chemical groups were used to analyse the influence of these groups on their adsorption capacities towards aromatic-type molecules whose adsorption is based on π-π interactions with surface arene centres. The three activated carbons studied were a low-functionalized carbon (Merck), an oxygen-rich carbon obtained by HNO3 oxidation of Merck, and a nitrogen-rich carbon also prepared from Merck by mild HNO3 oxidation followed by treatment with a dicyanodiamide/dimethyl formamide mixture at 300 °C. The nature of the surface chemical groups of the three activated carbons was investigated by both physical and chemical techniques (TPD, XPS, Boehm analysis and pH potentiometric titration). A systematic study of the adsorptions of a series of analogous aromatic adsorbates on the three activated carbons was carried out to study the adsorption mechanisms. In all cases the adsorption mechanism is based on π-π interactions between the aromatic moiety of the adsorbates and the arene centres of the graphite sheets. The differences in the normalized adsorption capacities of the adsorbents for a set of adsorbates indicate that the π-donor or π-withdrawing character of the functional groups have a clear influence on the basicity of the arene centres.

Caracterización de la impedancia de transferencia de materiales porosos-fibrosos usando holografía acústica de campo cercano (NAH)

En este trabajo se aplica la técnica de holografía acústica de campo cercano (NAH-Near field Acoustic Holography) para determinar la velocidad de vibración de la superficie de una capa de material absorbente que a su vez está adherido a una placa metálica circular que emula un pistón rígido. Este dato de la velocidad es necesario para predecir su impedancia de transferencia. En la experiencia propuesta, la placa metálica vibra por la acción de un actuador ubicado en su centro transmitiendo su vibración a la lámina porosa. El experimento y la técnica implementada se apoyan en la hipótesis del desacoplamiento de la parte vibratoria y la acústica de un sistema placa-poroso para determinar la eficiencia de radiación.

CeO2-promoted Ni/activated carbon catalysts for the water–gas shift (WGS) reaction

The low temperature water–gas shift (WGS) reaction has been studied over carbon-supported nickel catalysts promoted by ceria. To this end, cerium oxide has been dispersed (at different loadings: 10, 20, 30 and 40 wt.%) on the activated carbon surface with the aim of obtaining small ceria particles and a highly available surface area. Furthermore, carbon- and ceria-supported nickel catalysts have also been studied as references. A combination of N2 adsorption analysis, powder X-ray diffraction, temperature-programmed reduction with H2, X-ray photoelectron spectroscopy and TEM analysis were used to characterize the Ni–CeO2 interactions and the CeO2 dispersion over the activated carbon support. Catalysts were tested in the low temperature WGS reaction with two different feed gas mixtures: the idealized one (with only CO and H2O) and a slightly harder one (with CO, CO2, H2, and H2O). The obtained results show that there is a clear effect of the ceria loading on the catalytic activity. In both cases, catalysts with 20 and 10 wt.% CeO2 were the most active materials at low temperature. On the other hand, Ni/C shows a lower activity, this assessing the determinant role of ceria in this reaction. Methane, a product of side reactions, was observed in very low amounts, when CO2 and H2 were included in the WGS feed. Nevertheless, our data indicate that the methanation process is mainly due to CO2, and no CO consumption via methanation takes place at the relevant WGS temperatures. Finally, a stability test was carried out, obtaining CO conversions greater than 40% after 150 h of reaction.

Activated Carbons Impregnated with Na2S and H2SO4: Texture, Surface Chemistry and Application to Mercury Removal from Aqueous Solutions

The effects of treatment of an activated carbon with Sulphur precursors on its textural properties and on the ability of the complex synthesized for mercury removal in aqueous solutions are studied. To this end, a commercial activated carbon has been modified by treatments with aqueous solutions of Na2S and H2SO4 at two temperatures (25 and 140 °C) to introduce sulphur species on its surface. The prepared adsorbents have been characterized by N2 (-196 °C) and CO2 (0 °C) adsorption, thermogravimetric analysis, temperature-programmed decomposition and X-ray photoelectron spectroscopy, and their adsorption capacities to remove Hg(II) ions in aqueous solutions have been determined. It has been shown that the impregnation treatments slightly modified the textural properties of the samples, with a small increase in the textural parameters (BET surface area and mesopore volumes). By contrast, surface oxygen content was increased when impregnation was carried out with Na2S, but it decreased when H2SO4 was used. However, the main effect of the impregnation treatments was the formation of surface sulphur complexes of thiol type, which was only achieved when the impregnation treatments were carried out at low temperature (25 °C). The presence of surface sulphur enhances the adsorption behaviour of these samples in the removal of Hg(II) cations in aqueous solutions at pH 2. In fact, complete Hg(II) removal is only obtained with the sulphur-containing activated carbons.