Nanomaterials have received increasing attention during the last decades in the solid state field since they play a major role as catalyst and catalyst supports for many applications including fuel cells or gas sensors. The interest is mainly due to their high specific surface area, which leads to an increase of performance and a cost-effective solution for expensive or rare materials. However, many studies have reported the collapse of nanostructures at high temperature as one of the main drawbacks for their implementation in real devices and therefore, routes to thermally stabilize these materials must be explored. In this thesis, the unique features of ordered mesoporous materials fabricated by nanocasting are exploited to create quasi-universal thermal stabilization methodologies, allowing implementing and evaluating them in high temperature energy applications e.g. solid oxide fuel cells. The work developed is divided into seven parts. The first chapter introduces the basics of mesoporous materials, solid oxide fuel cells, catalysis and gas sensors. The second chapter focuses on the experimental procedures and the characterization tools employed. In the third chapter, a novel route to thermally stabilize 3-D open mesoporous structures is presented. The next three chapters, show the fabrication and evaluation of thermal stable mesoporous materials as electrodes for solid oxide fuel cells. Finally, chapter seven presents the suitability of mesoporous ceramic oxides as functional materials in humidity sensors. / Los nano-materiales han recibido especial atención durante estas últimas décadas en el campo del estado sólido dado el importante papel que desempeñan como catalizadores y/o soportes catalíticos en diversas aplicaciones, tales como las pilas de combustible o los sensores de gas. Este interés se debe principalmente a su elevada área específica, que da lugar a una mejora del rendimiento y es una solución efectiva para aquellas aplicaciones que requieran materiales de elevado coste. Sin embargo tal y como señalan muchos estudios, el colapso de estas nano-estructuras a elevadas temperaturas es uno de los mayores inconvenientes para su implementación en dispositivos reales, siendo por tanto necesario explorar nuevas rutas que consigan estabilizar estos materiales térmicamente. El objetivo de la presente tesis es desarrollar metodologías cuasi-universales de estabilización térmica, mediante la explotación de las características exclusivas que poseen los materiales mesoporosos ordenados fabricados a partir de un template. Lo cual nos permite implementarlos y evaluarlos en aplicaciones energéticas que operan a elevada temperatura p.ej. pilas de combustible de óxido sólido. El trabajo desarrollado se divide en siete partes. El primer capítulo introduce los fundamentos de los materiales mesoporosos, las pilas de combustible de óxido sólido, la catálisis y los sensores de gas. En el segundo capítulo se detallan los procedimientos experimentales y las técnicas de caracterización empleados. El tercer capítulo presenta una nueva metodología para estabilizar térmicamente los materiales mesoporosos de estructura 3-D abierta. Los siguientes tres capítulos, muestran la fabricación y el comportamiento electroquímico de materiales mesoporosos térmicamente estables trabajando como electrodos de pilas de combustible de óxido sólido. Por último, en el capítulo siete se demuestra la viabilidad de los óxidos cerámicos mesoporosos como materiales funcionales en sensores de humedad.

Esta tesis doctoral resume el trabajo realizado en el Departamento de Electrónica de la Facultad de Física, en la Universidad de Barcelona. El objetivo de la misma se centra en el diseño y fabricación de un microsistema óptico basado en la integración híbrida de componentes comerciales y procesos de micromecanizado en silicio, destinado a la detección óptica de micropartículas en chips de microfluídica. Todo ello teniendo como principales metas la miniaturización y la integración de todos los componentes para obtener un sistema robusto, portátil, orientado a aplicaciones “Point of care”. El sistema de detección óptica de partículas incluye dos elementos comerciales. Por una parte, las fuentes de luz escogidas, láseres VCSEL en formato “die” de la empresa ULM Photonics, y por otra, una matriz de microlentes fabricada por SUSS microOptics. La matriz de microlentes se adapta al pitch que existe entre láseres es de 250 micras, cosa que la hace totalmente compatible en términos de alineación óptica. Para determinar las posiciones óptimas de estos componentes, se realiza el estudio de dos escenarios mediante el uso de un simulador de trazado de rayos (ZEMAX Radiance ®): el primero, basado en la obtención de haces de luz colimados; el segundo, basado en la obtención de haces de luz focalizados. Los componentes comerciales se ensamblan en una estructura robusta, formada por dos piezas de silicio (base y separador óptico), y con alienación pasiva de las microlentes. Las piezas de silicio se fabrican en obleas siguiendo procesos de Sala Blanca. Mediante técnicas de soft lithography se diseñan y fabrican diversos chips para el bloque de microfluídica: canales con focalización pasiva del flujo y canales con sistemas de focalización activa. Dichos chips contienen los canales de microfluídica por donde circularán las partículas que se pretende detectar, en suspensión líquida. El sistema de detección óptica de partículas requiere de un sensor óptico encargado de detectar las variaciones en los niveles de intensidad luminosa causadas por la circulación de partículas. En esta tesis se plantea un sensor de imagen basado en tecnología CMOS, con un diseño full-custom. El sensor contiene una estructura en doble array lineal con 256 pixels. Para validar la funcionalidad del sistema fabricado, se realizó una batería de pruebas. Se prepararon diversas suspensiones acuosas en agua desionizada e isopropanol con partículas de diferentes tamaños (diámetros), materiales y fabricantes en un rango de 10 a 90micras de diámetro. Los resultados fueron satisfactorios en todos los casos. / This thesis summarizes the work developed in the Department of Electronics, Faculty of Physics, at the University of Barcelona. This work is focused on the design and fabrication of an optical microsystem based on hybrid integration of commercial components and silicon micromachining processes, in order to the optical detection of microparticles in microfluidic chips. Main goals are the miniaturization and integration of all components to obtain a robust system, portable, and oriented to "Point of care" applications. The optical detection system includes two commercial components. First, the chosen light sources, VCSEL lasers in "die " format from ULM Photonics, and second, an array of microlenses manufactured by SUSS microoptics. The microlens array fits the existing pitch between lasers (250 microns), therefore it is fully compatible in terms of optical alignment. To determine the optimal positions of these components, two scenarios are analyzed by using a ray tracing simulator (ZEMAX Radiance ®): the first, based on collimated light beams, the second based on obtaining focused light beams. The commercial components are assembled in a robust structure, consisting of two pieces of silicon (base and optical spacer), and passive alignment of the microlenses. The pieces of silicon are fabricated in wafers at the clean room of the IBM-CNM, according to the defined processes. Using soft lithography techniques, various chips for the microfluidic block are designed and fabricated: passive focusing channels and channels with hydrodynamic focusing. These chips contain microfluidic channels where particles to be detected will flow in liquid suspension. The optical detection system requires an optical sensor to detect the variations in the levels of light intensity caused by the particles circulation. In this thesis, an image sensor based on CMOS technology and a full-custom design is presented. The sensor includes a double linear array structure with 256 pixels and other electronics. To validate the functionality of the proposed system, we performed a battery of tests. Several aqueous suspensions were prepared in deionized water and isopropanol with particles of different sizes (diameters) materials and manufacturers in the range of 10 to 90micras diameter. The results were satisfactory in all cases.

The objective of this thesis is to present a proposal for the analogue signal processing chain needed for the LHCb calorimeter upgrade improving the design used originally. The design contains several novelties: the system was designed with low noise in mind from the beginning, it is made to have good immunity to interferences stressing the fact that the board will be shared with large digital circuits, differential operational amplifiers are used in a non-standard way as a mean to obtain opposite polarity signals for the signal treatment and a way to increase the available signal in the front end electronics is proposed. The thesis starts with a brief introduction to the detector and its environment. This is followed by an explanation of the use of shapers in high energy physics detectors and the constraints that the shaper must address in the LHCb calorimeter. This leads to a chapter where the circuit design is explained starting from the analysis of the original circuit and its flaws. Once the original circuit and the restrictions are understood the different parts of the circuit are explained showing the key points of each one. The explanation always starts as theoretic calculations, followed by practical problems and its solution until a fine tuning is obtained. Once the functional circuit is designed a chapter of electromagnetic considerations explains all the measures taken during the PCB design to prevent noise from leaking into the system. Stability and noise issues are discussed in depth in the last theoretic chapters. After that the different measurement procedures and results are exposed followed by the conclusions. / La presente tesis doctoral versa sobre una propuesta para la actualización del sistema de tratamiento analógico de la señal procedente del calorímetro de LHCb. El esquema propuesto incluye diversos elementos diferenciadores: ha sido diseñado específicamente para minimizar el ruido electrónico y coexistir en la misma placa de circuito impreso que la lógica digital minimizando la contaminación por el ruido que esta genera; utiliza amplificadores operacionales de un modo no convencional para conseguir señales de polaridades opuestas con gran precisión y propone un método para maximizar la carga entregada a la electrónica en el caso particular del calorímetro de LHCb. El documento arranca con una introducción al experimento, los denominados shapers y su utilización el física de altas energías para luego describir en detalle las fases de diseño, prototipado y medición de resultados haciendo especial hincapié en la compatibilidad electromagnética, la integridad de señal y la minimización del ruido.

In this thesis we study and characterize the behavior of Bose-Einstein condensates in a BJJ, using two different theoretical formalisms: the mean-field approximation (with the Gross-Pitaevskii equation) and many-body calculations (based on Bose-Hubbard models). With single-component Bose-Einstein condensates, we have focused on the study of the structure of the ground state as a function of the system parameters. We have looked for strongly correlated states, that cannot be described with mean-field theories, and we have proposed a variational wave function that captures the structure of the ground state for a broad interval of the system parameters. We have also studied the nonlinear effects of the Gross-Pitaevskii equation, visible when atom-atom interactions are strong. In the case of binary mixtures of Bose-Einstein condensates we have performed an intensive study of the different regimes that can arise and in which conditions. The standard two-mode approximation is one of the most used in the study of the Josephson effect, as it gives simple analytic equations that capture, to a great extend, the behavior of the system. When the link between condensates is not weak enough, one has to consider a correction to this approximation, namely, the improved two-mode approximation. In this thesis, we have derived this last approximation for the binary mixture and we have checked its validity comparing it with numerical simulations of the three-dimensional Gross-Pitaevskii equation. Moreover, as the Josephson dynamics is almost one-dimensional, we have considered the two most common reductions of the dimensionality of the Gross-Pitaevskii equation. In this case, we have also compared, using simulations, these one-dimensional reductions with the three-dimensional equation. We have also studied spinor condensates in an external BJJ. We have focused on condensates formed by atoms with spin $F=1$, which can be in any of the three internal states $m_F = 0, \pm 1$. Furthermore, in contrast to the binary mixture, spin interchange is allowed, so that the number of particles of each component becomes a dynamic variable. First, we have studied this system within the mean-field framework, using the Gross-Pitaevskii equation. We have derived the two-mode approximation equations and we have focused in studying the decoupling of the Josephson effect and the population transfer dynamics. In this case, we also compare the results with numerical simulations of the three dimensional Gross-Pitaevskii equation. Second, we have studied the spinor BJJ using the Bose-Hubbard formalism, because some features of quantum fluctuations are better captured than with the mean-field. We have characterized the ground state, paying special attention to the regions where it is strongly correlated. We have seen how the spin singlet formation (strongly correlated state between two particles) affects the structure of the ground state. Finally, we have studied finite temperature effects on spinor Bose-Einstein condensates in the presence of a magnetic field, for two different cases. First, we have analyzed a condensate formed by $F=1$ atoms with contact interactions. We have considered that the condensate was formed by atoms in the internal state $m_F=0$ and we have studied the dependence of the fluctuations of the other two components $m_F = \pm 1$ as a function of temperature. We have used the Bogoliubov formalism applied to an homogeneous system, and then, we have generalized the result to an harmonic trap by using the local density approximation. Second, we have studied a condensate formed by particles with $F=3$ with contact interactions and moreover, dipolar interactions. In a similar way as the previous case, we consider that the condensate is formed by particles with $m_F =-3$ and we study the fluctuations in $m_F = -2$ and $m_F = -3$. / En aquesta Tesi s'estudia i es caracteritza el comportament dels condensats de Bose-Einstein en una junció bosònica de Josephson (BJJ), tot utilitzant dos formalismes teòrics diferents: l'aproximació de camp mig (amb l'equació de Gross-Pitaevskii) i càlculs de molts cossos (basats en models de Bose-Hubbard). En condensats d'una sola component, ens hem centrat en l'estudi de l'estructura de l'estat fonamental en funció dels paràmetres del sistema. Hem identificat estats altament correlacionats que no es poden descriure amb teories de camp mig, i hem proposat una funció d'ona variacional que captura l'estructura de l'estat fonamental en un ampli ventall de valors d'aquests paràmetres. També hem estudiat els efectes no lineals de l'equació de Gross-Pitaevskii, visibles quan les interaccions entre àtoms són fortes. Per condensats formats per dues components hem fet un estudi intensiu dels diferents règims que es poden formar i en quines condicions. Hem utiltizat el formalisme de camp mig i hem derivat l'aproximació bimodal estàndard millorada (I2M) tot comprovant-ne la seva validesa, comparant-la amb simulacions numèriques de l'equació de Gross-Pitaevskii tridimensional. També hem estudiat condensats espinorials en una BJJ externa. Ens hem centrat en condensats formats per àtoms amb spin $F=1$, que poden estar en qualsevol dels tres estats interns $m_F=0,\pm 1$. Primer, hem estudiat aquest sistema dins la teoria de camp mig, tot utilitzant l'equació de Gross-Pitaevskii. Hem derivat les equacions de l'aproximació bimodal, i ens hem centrat en estudiar com es desacobla l'efecte Josephson de la dinàmica d'intercanvi de partícules. Segon, hem utilitzant el formalisme de Bose-Hubbard i hem caracteritzat l'estat fonamental, tot fixant-nos en els effectes de la creació de singlets. Finalment, hem estudiat l'efecte de temperatura finita en condensats de Bose-Einstein espinorials en presència d'un camp magnètic, per dos casos ben diferenciats: 1) un condensat amb $F=1$ i interaccions de contacte i 2) un condensat amb $F=3$ i interaccions de contacte i dipolars. Per a tots dos cassos, proposem un mètode per fer termometria a molt baixes temperatures, i un mètode per refredar el sistema tot variant el camp magnètic extern.

Promising technological applications of two-phase flows in space have captured the increasing interest of the space sector, provoking a strong demand for more fundamental knowledge. Great efforts have been made in recent decades to study the behavior of two-phase flows in low-gravity environments, which is expected to be different than the behavior observed in the presence of gravitational forces. Nevertheless, many phenomena are still poorly understood. The development of any of these new technologies demands a better knowledge of two-phase flows. In this manuscript we address questions regarding the generation of gas-liquid flows and their behavior in conditions relevant for a microgravity environment. In particular, we focus on an air-water mixture formed in a capillary T-junction. To this end, an experimental setup has been designed to accurately control both gas and liquid flow rates. We performed a quantitative characterization on ground of the T-junction, whose operation is robust to changes in gravity level. Its main performance is the generation of bubbles at a regular frequency with small size dispersion. We obtained two working regimes of the T-junction and identified the crossover region between them. Bubble, slug, churn and annular flow regimes have been observed during the experiments and a flow pattern map has been plotted. We present an experimental study on the bubble-slug transition in microgravity-related conditions. In addition, we address questions regarding the existence of a critical void fraction in order for the bubble-slug transition to occur. The gas-liquid flow has been characterized by measuring the bubble generation frequency as well as the bubble and liquid slug sizes. Since bubble dynamics is also expected to be different in the absence of buoyancy, the bubble velocity has also been studied. The mean void fraction appears as one relevant parameter that allows for the prediction of frequency, bubble velocity, and lengths. We propose curves obtained empirically for the behavior of generation frequency, the bubble velocity and the lengths. The dependence of the frequency on the Strouhal dimensionless number has been analyzed. A numerical study of the formation of mini-bubbles in a 2D T-junction by means of the fluid dynamics numerical code JADIM is also presented. Simulations were carried out for different flow conditions, giving rise to results on the bubble generation frequency, bubble velocity, void fraction and characteristic lengths. Numerical results have been then compared with experimental data.

Water is commonly associated with life. This substance affects the living beings in countless aspects and length scales, ranging from molecular biology to climatology. Water exhibits a long series of anomalous behaviors. These anomalies can be rationalized as a consequence of a second critical point in the supercooled region of the liquid phase. Nevertheless, the large part of the phase diagram of supercooled water is to date experimentally inaccessible for the inevitable crystallization of the bulk liquid. Confinement of water in nano-structures is a possible way to prevent the crystallization of molecules. In this thesis we present a coarse-grain model to describe the physical behavior of water at hydrophobic interfaces. The essential feature of the model is the description of water-water interaction via directional and cooperative components of the hydrogen bond (HB). We explore the phase diagram of supercooled water nano-confined between hydrophobic walls. Our results, grounded in statistical physics methods and Monte Carlo simulations, show the presence of a line of first order phase transition in the temperature-pressure plane separating two liquid phases and ending in a liquid-liquid critical point (LLCP). The LLCP universality class approaches the one of the Ising model in two dimensions in the thermodynamic limit, while large deviations are observed for strong confinement. Below the LLCP we find the locus of maxima of correlation length (the Widom line) of the system. Near the LLCP we find a large increase of the thermodynamic response functions consistent with the anomalous behaviors of water. These predictions are confirmed by a percolation description of water molecules based on the definition of cluster of correlated degrees of freedom. Along the phase transition line and the Widom line we recover a power law cluster distribution. At the LLCP the scaling of the percolation quantities agree with the Ising critical exponents. The density, energy and entropy fluctuations that are at the base of the anomalies of water and the existence of its LLCP have also consequences in the context of protein stability. General thermodynamic prediction asserts the existence of a close stability region (SR) in temperature-pressure plane for the native folded state of a protein. Experimental evidences support this theory showing hot-, cold- and pressure-denaturation. Water behavior at the protein interface is expected to be the driving force for the folding-unfolding process. To shed light on this mechanism we study the SR of a folded hydrophobic polymer solvated in the coarse-grain water. Tuning the water-water interaction at the interface and the density of the hydration shell we find an elliptic protein SR in the temperature-pressure plane, qualitatively consistent with available experimental data. Our work contributes to the ongoing debate about the role of hydration water in stabilizing the native protein state. We show here that the physics of water, and in particular its energy, density and entropy fluctuations are sufficient to rationalize the existence of a protein SR with respect to temperature and pressure. / El agua es, probablemente, el líquido más importante para la vida. Afecta el clima y la morfología de la Tierra, es fundamental en muchas tecnologías y desarrolla un papel fundamental en los procesos biológicos. A pesar de su importancia y abundancia su comportamiento sigue siendo difícil de entender respecto a los fluidos simples, del tipo argón (el agua tiene más de sesenta anomalías). En esta tesis proponemos un modelo de grano-grueso capaz de captar algunas características microscópicas de la interacción agua-agua en una interfaz hidrofóbica. Hemos analizado el diagrama de fases por baja temperatura de una mono-capa de agua confinada entre paredes paralelas hidrófobas encontrando un punto crítico líquido-líquido en la región sobre-enfriada, al final de una línea de transición de primer orden entre dos fases líquidas. El punto critico pertenece a la clase de universalidad Ising en dos dimensiones sólo por tamaño de las paredes muy grandes. Sorprendentemente, aumentando el confinamiento, la clase de universalidad desvía hacia la de Ising en tres dimensiones. Presentamos una descripción geométrica de la región de moléculas correladas en la monocapa sobreenfriada. Nuestros resultados enseñan que la línea de transición líquido-líquido y la línea Widom (su continuación analítica) se caracterizan por una línea de percolación, donde la distribución de los clúster decae según ley de potencia. Esta línea marca la región donde las fluctuaciones de puentes de hidrógeno se extienden por toda la red. Finalmente hemos estudiado cómo la red de puentes de hidrógeno puede estabilizar el estado nativo de una proteína, en función de la variación de la interacción agua-agua en la interfaz hidrofóbica y del aumento de densidad del agua interfacial al aumentar la presión. El modelo muestra que la proteína se desnaturaliza a alta y baja temperatura, y a alta y a baja presión, reproduciendo las características de desnaturalización observadas en los experimentos. La región de estabilidad de la proteína, tiene una forma elíptica de acuerdo con la teoría.

Esta tesis se enfoca en el crecimiento y caracterización estructural y funcional de capas finas de carburo de cromo, con el fin de establecer las relaciones entre la síntesis, estructura y propiedades. La tecnología de depósito empleada en este estudio fue el arco catódico filtrado a partir de un blanco de cromo en una atmósfera reactiva de argón y acetileno (Ar + C2H2). Además, se diseñó un filtro lineal magnético para reducir el número de macropartículas que se depositan en las capas y que son inherentes al proceso de arco catódico. Las capas se depositaron sobre diferentes tipos de sustratos, silicio, vidrio y acero con el fin de realizar diferentes caracterizaciones. Las principales caracterizaciones realizadas fueron espectroscopias de foto-electrones de rayos-X (XPS), Raman y de infra-rojo (FTIR), difracción de rayos-X (XRD), microscopia de transmisión electrónica (TEM), así como nanoindentación y ball-on disk. Durante el desarrollo de esta tesis se ha logrado obtener por primera vez estructuras nanocompuestas formadas por nanocristales de carburo de cromo embebidas en una matriz de carbono amorfo hidrogenado, nc-CrC/a-C:H, y también estructuras nanocompuestas formadas por nanocristales de cromo embebidas en una matriz de carburo de cromo amorfo, nc-Cr/a-CrC depositadas por medio de la técnica de arco catódico filtrado. Se analizó principalmente el efecto de la presión total y presión parcial de acetileno y el voltaje de polarización aplicado a los sustratos sobre la composición química y la microestructura de las capas. Los parámetros con mayor influencia en la composición química de las muestras resultaron ser la presión total y la presión parcial de acetileno, lo que permitió obtener capas con contenidos de carbono desde 13.1 hasta 72.4 at.%. El voltaje de polarización tuvo también una gran importancia en la composición química pero se encontró que principalmente tiene una fuerte influencia en la estructura cristalina de las capas. Las capas depositadas a altas presiones, 6•10-2 mbar, y ricas en carbono presentaron una estructura amorfa y/o con estructura de nanocompuesto consistente en nanocristales de carburo de cromo embebidos en una matriz de carbono amorfo hidrogenado, nc-CrC/a-C:H. Las capas depositadas a una presión intermedia, 3•10-2 mbar, presentaron composiciones químicas cercanas a la estequiometria del Cr3C2 y estructuras amorfas, nanocompuestas o altamente cristalinas en función del voltaje de polarización. Las capas depositadas a baja presión, 6•10-3 mbar, y ricas en cromo presentaron estructuras amorfas, estructuras nanocompuestas consistentes en nanocristales de cromo embebidos en una matriz de carburo de cromo amorfo, nc-Cr/a-CrC, y estructuras altamente cristalinas en función del voltaje de polarización. Las capas presentaron diferentes combinaciones de dureza y coeficientes de fricción en función del contenido de carbono. Las capas depositadas a altas presiones y que fueron ricas en carbono presentaron los mejores valores de coeficientes de fricción, hasta 0.15, combinados con relativamente bajos valores de dureza, entre 3 y 8 GPa. Las capas depositadas a una presión intermedia, con composiciones químicas cercanas a la estequiometria del Cr3C2 presentaron los mejores resultados de dureza, hasta 33 GPa y a su vez buenos resultados de coeficiente de fricción, del orden de 0.3. La combinación de buenas propiedades mecánicas y tribológicas proporciona un material en forma de capa fina con un futuro prometedor para el desarrollo de aplicaciones mecánicas, tribológicas y biomédicas. / This thesis is focused in the growth and structural and functional characterization of chromium carbide thin films with the aim to establish synthesis, structure and property performance relations. The deposition technique employed in this study was filtered cathodic arc from a chromium target in a reactive argon and acetylene atmosphere. A linear magnetic filter was designed in order to reduce the macroparticles that reach the substrates and that are inherent to the cathodic arc process. During the development of this thesis it was reported for the first time the deposition of nanocomposite structures of chromium carbide nanocrystals embedded in an amorphous hydrogenated carbon matrix, nc-CrC/a-C:H, and also nanocomposite structures of chromium nanocrystals embedded in an amorphous chromium carbide matrix, deposited by filtered cathodic arc technique. The main parameters that influenced the chemical composition of the samples were the total pressure and acetylene partial pressure. The bias voltage also had a remarkably effect on the chemical composition, but it was found that it affects mainly to the crystalline structure of the films. The films deposited at high total pressure, 6•10(-2) mbar, were rich in carbon and presented an amorphous and/or nanocomposite structure consisting of chromium carbide nanocrystals embedded in an amorphous hydrogenated carbon matrix, nc-CrC/a-C:H. The films deposited at intermediate pressure, 3•10(-2) mbar, presented compositions near to the Cr(3)C(2) stoichiometry and amorphous, nanocomposite or highly crystalline structures as function of the bias voltage. The films deposited at low pressure, 6•10(-3) mbar, were rich in chromium and presented amorphous or nanocomposite structures consisting of chromium nanocrystals embedded in an amorphous chromium carbide matrix, nc-Cr/a-CrC. The films presented different combinations of hardness and friction coefficient as function of the carbon content. The films rich in carbon, presented the lower friction, combined with a relatively low hardness. The films deposited with compositions near to the Cr(3)C(2) stoichiometry, presented the highest hardness, and good results of friction. The combination of excellent mechanical and tribological properties provides materials with a promising future for mechanical, tribological and biomedical applications.

Multiferroic materials, in which both ferroelectric and (anti)ferromagnetic orders coexist in the same phase, have received much interest in the last few years. The possibility of these two ferroic orders being coupled allows new functionalities in these materials as controlling the magnetisation by an electric field or, conversely, controlling the polarisation by a magnetic field. The fulfilment of this magnetoelectric coupling is not only interesting in terms of fundamental research but it would also pave the way for designing novel magnetoelectric applications. For this latter purpose, ferromagnetic multiferroics would have greater advantages over the antiferromagnetic ones because of the net magnetisation. However, it is the antiferromagnetic order which prevails in multiferroic materials. Bi-based perovskite and double-perovskite oxides, BiBO3 and Bi2BB’O6, respectively, where B and B’ are magnetic transition metal ions present an excellent starting point to investigate new ferromagnetic ferroelectric materials. In these compounds ferroelectricity arises from the stereochemical activity of Bi3+ cations. Conversely, magnetism is driven by the superexchange interaction between the magnetic ions through the adjacent oxygen ions (B – O – B). In particular, to date, BiMnO3 and Bi2NiMnO6 systems are the only reported ferromagnetic Bi-based perovskite oxides. Hence, both systems are investigated in the work of this thesis in thin films . First of all, this thesis addresses the synthesis of these compounds. In this process, three main hindrances were met. Firstly, these Bi-based compounds are highly metastable, which implies that they are only possible to be synthesised in bulk under extreme conditions, i.e. under high temperatures and high pressures. The strategy used to circumvent the required high pressures consisted of replacing the mechanical pressure by the epitaxial stress in thin films. For this purpose these Bi-based compounds were grown by pulsed laser deposition (PLD) onto single-crystal (001)-oriented SrTiO3 substrates. Secondly, Bi is a highly volatile element and consequently the synthesis temperature was not a free deposition parameter, forcing the use of low synthesis temperatures in order to prevent non-stoichiometric films or even the no-formation of the compound when the Bi-deficiency was too large. Yet the general metastable character of these compounds demands the use of high temperatures to the synthesis process. These two antagonistic requirements were tried to be balanced by using 10% Bi-rich PLD targets in the case of BiMnO3 system and by partial replacement of Bi3+ cations by La3+ cations (by 10%) in the case of Bi2NiMnO6 system. In the latter approach, La-doping gives rise to a slightly reduced unit cell volume, exerting the socalled chemical pressure which contributes to prevent Bi3+ cations from desorption during the growth process. Thirdly, both in the ternary Bi – Mn – O and quaternary Bi – Ni – Mn – O systems a strong multiphase formation tendency was found, especially in the former, in which apart from the desired BiMnO3 and Bi2NiMnO6 compounds, different parasitic oxide phases appeared in the grown films. As a consequence of all these facts the single-phase stabilisation of either BiMnO3 or (Bi0.9La0.1)2NiMnO6 was greatly hampered and only possible to be achieved under a narrow window of deposition conditions. Once the deposition conditions for single-phase stabilisation of the Bi-based compounds are controlled, structural characterisation proves that both BiMnO3 and (Bi0.9La0.1)2NiMnO6 grow fully coherent on SrTiO3 substrates, thus adopting as the inplane lattice parameter that of the cubic substrate and subsequently a tetragonal-like structure. Importantly enough for the magnetic properties, (Bi0.9La0.1)2NiMnO6 thin films are found to display long-range B-site order and the Ni2+/Mn4+ electronic configuration, which is the required condition for a long-range ferromagnetism. Indeed, ferromagnetic behaviour is recorded but with a reduced Curie temperature probably due to the epitaxial strain of the substrate. Instead, BiMnO3 thin films are found to exhibit similar Curie temperature to that of bulk specimens. Two-dimensional growth mode is obtained for (Bi0.9La0.1)2NiMnO6 thin films, attaining very low rough surface, whereas BiMnO3 thin films were in all cases displaying a clear three-dimensional growth mode, yielding rougher surface morphology. Finally, in order to study the dielectric/resistive, magnetoelectric and ferroelectric properties parallel-plate capacitors were fabricated using single-crystal (001)-oriented Nb doped SrTiO3 substrates as bottom electrode and sputtered Pt as top electrodes. In (Bi0.9La0.1)2NiMnO6 thin films ferroelectric domains switching current is measured, which allows conclusively stating that (Bi,La)2NiMnO6 compounds are indeed ferroelectric up to at least 10% La content. By structural characterisation the ferroelectric transition temperature is inferred to be around 450 K. The second part of this bloc is devoted to study the dielectric properties and the possible magnetoelectric coupling of these compounds. In this work both the dielectric response and the magnetoelectric response was assessed by impedance spectroscopy, the latter using magnetic fields while recording the impedance response, with the final aim of observing any deviation of the dielectric permittivity of these compounds either in the vicinity of the ferromagnetic transition temperature or when applying a magnetic field. Either phenomenon would indicate magnetoelectric coupling. Special attention is given to the conventional artefacts these measurements often produce when performed on dielectric thin films, causing misleading interpretations, like apparent colossal dielectric constants and/or apparent large magnetoelectric couplings. Following these precautions the intrinsic dielectric and magnetoelectric response of BiMnO3 and (Bi0.9La0.1)2NiMnO6 thin films are extracted. Despite the fact that BiMnO3 dielectric data shows clear magnetoelectric signs, results points to a weak magnetoelectric coupling, which is especially emphasised in (Bi0.9La0.1)2NiMnO6 thin films, probably driven by the fact that magnetism and ferroelectricity arise by two independent mechanisms in these Bibased compounds. / Los materiales multiferroicos, en los cuales coexisten en la misma fase un ordenamiento ferroeléctrico y magnético, han recibido mucho interés en los últimos años. La posibilidad de que estén acoplados los dos órdenes ferroicos permite nuevas funcionalidades en estos materiales como el control eléctrico de la magnetización o, por el contrario, el control magnético de la polarización. La realización de dicho acoplamiento magnetoeléctrico no solo sería interesante en términos de investigación básica, sino que abriría camino para el diseño de nuevas aplicaciones magnetoeléctricas, especialmente en el campo de la spintrónica, como filtros de spin o uniones túneles magnéticas controladas mediante campos eléctricos en lugar de campos magnéticos y por lo tanto promoviendo una nueva generación de dispositivos de almacenamiento de alta densidad y bajo consumo. Para este último propósito, los multiferroicos que poseen un ordenamiento ferromagnético tendrían mayores ventajas que aquellos antiferromagnéticos debido a que los primeros mostrarían magnetización neta y por lo tanto permitirían un control más fácil del estado magnético. No obstante, es el orden antiferromagnético el que prevalece en estos materiales. Por eso es necesario la búsqueda de nuevos materiales que sean ferromagnéticos y ferroeléctricos. Los óxidos en estructura perovskita y doble perovskita basados en Bi, BiBO3 y Bi2BB’O6, respectivamente, donde B y B’ son iones magnéticos de metales de transición (es decir, con la capa electrónica externa d parcialmente ocupada), presentan un excelente punto de partida para investigar nuevos materiales ferromagnéticos y ferroeléctricos. En primer lugar, esta tesis aborda el problema de sintetizar estos compuestos. En este proceso se topó con tres principales obstáculos. Primero, estos compuestos basados en Bi son altamente metaestables, lo que implica que en su forma masiva sólo se pueden sintetizar bajo condiciones extremas: altas temperaturas y altas presiones (del orden de los GPa). Segundo, Bi es un elemento altamente volátil y por consiguiente la temperatura de síntesis de estos compuestos no fue un parámetro de crecimiento libre. Tercero, tanto en el sistema ternario Bi – Mn – O como cuaternario Bi – Ni – Mn – O se encontró una fuerte tendencia multifásica, especialmente en el primero, en los cuales, aparte de los compuestos deseados BiMnO3 y Bi2NiMnO6, se forman diferentes fases parásitas de óxidos como Mn3O4, Bi2O3 y MnO2 en el primer caso y NiO en el segundo. Como consecuencia de todos estos factores la estabilización monofásica de tanto BiMnO3 como (Bi0.9La0.1)2NiMnO6 fue dificultada en gran medida y solo se pudo conseguir bajo una ventana estrecha de condiciones de crecimiento. Especialmente crítico fue la temperatura de depósito, la cual sólo permitía una ventana de 10ºC alrededor de 630ºC y 620ºC para la síntesis de BiMnO3 y (Bi0.9La0.1)2NiMnO6, respectivamente.

Tesi realitzada a l'Institut de Recerca Energètica de Catalunya (IREC) / Bona part dels processos naturals i de les activitats humanes impliquen processos de transferència d’energia, que en part, o en la seva totalitat es dissipen en el medi. L’aprofitament de l’energia residual present en l’ambient (Energy harvesting), principalment en forma tèrmica, cinètica o solar, per produir energia elèctrica constitueix una fita rellevant per assolir sistemes plenament autònoms. Les energies residuals del medi, són fonts d’energia que fluctuen en el temps, si no es poden aprofitar al moment es perden, per aquest motiu, els sistemes per emmagatzemar l’energia elèctrica produïda tenen una gran importància a l’hora de garantir el funcionament d’un sistema plenament autònom. En aquest treball s’ha proposat: 1.-Estudiar els sistemes de captació i conversió d’energia residual a elèctrica basats en propietats funcionals, essencialment focalitzades per captació d’energia tèrmica, mecànica i solar, obtingudes en materials nano estructurats, processats per fabricar, utilitzant tecnologies d’obtenció de dispositius multicapes, sistemes compatibles amb la seva integració en sistemes portables. 2.-Desenvolupar un nou sistema d’emmagatzematge elèctric basats en tecnologies de capa prima i compatible amb els sistemes de captació i conversió a energia elèctrica que es desenvoluparan, es proposa el disseny i fabricació de prototips funcionals de supercondensadors com a substituts de les bateries convencionals. 3.-Desenvolupar aplicacions portables, incloent-hi el seu control i les associades comunicacions, centrades en aquelles integrables en sistemes personals, especialment en la vestimenta de persones, tanmateix el sistema ha de permetre la mesura continuada de paràmetres mediambientals. 4.-Realitzar proves de camp per la validació dels prototipus per ambients i entorns intel·ligents / Most of natural phenomena and today´s society-induced routine operations involve energy transfer processes in which part of the energy, if not all, is irreversibly lost. Suitable methods to efficiently capture and convert this unused energy into electricity may have an important role for the development of a broad range of applications, i.e. battery replacement in miniaturized devices, autonomous robots, or sensors operating in remote. Energy storage is a critical question to obtain a complete autonomous system. In the present work a new storage system based in electrochemical double layer capacitor has been developed and tested in field applications. It’s has been used into smart sensor network with an efficient Energy management. Sunlight is the major source of renewable energy, a lot of efforts have been devoted to study and improve the energy conversion from sunlight to electric power, also, light and thermal from human activities constitute another source of unused power. Related to kinetic, environmental vibrations and/or motions caused by wind, high waters, waves, industrial and traffic activities, have been identified among the major sources of unused power. These sources constitute ideal inputs for piezoelectric materials which have the ability to convert mechanical energy into electrical energy with high conversion efficiency. Textile materials are commonly used in large-area industrial, engineering, architectural, clothes and transport applications, where they are subjected to large amounts of motion, vibration, torsion and strain. Thus, textiles appear as optimum structures to implement piezoelectric systems for large-area scavenging, storage and transmission of electric energy. This research looks to: 1. -Study the different parts involved in energy harvesting, looking for the applications of nanomaterials to manufacture the transducers and the energy storage devices. 2. -Design and develop a new energy storage systems based on electrochemical double layer capacitor (EDLC) related to the energy harvesting devices proposed. 3. -To develop a complete autonomous, low power network system as a proof of concept. 4. -Make field test with the prototypes developed in order to verify the technical feasibility of the energy harvesting system.

This thesis aims at providing a better understanding of the micro- and nanofabrication of conducting polymers for biomedical devices and presents novel processes that widen the application range of conducting polymers in this field. The thesis is divided in four chapters, namely “Materials and Methods”, “Biocatalytically-produced polypyrrole thin films and microelectrodes on insulating surfaces”, “Azide-PEDOT electrodes. Application to DNA sensors” and “Fabrication of polypyrrole single nanowire devices”. Chapter 1, entitled “Materials and Methods”, describes the materials used in this work and the fabrication and characterization methods required for the development of the thesis. Here, theoretical and experimental details about the techniques employed, are provided. Chapter 2, entitled “Biocatalytically-produced polypyrrole thin films and microelectrodes on insulating surfaces”, presents a new on-surface biocatalytical procedure for the fabrication of polypyrrole microelectrodes on insulating surfaces, with resolutions comparable to the ones of conventional photolitography. This is an environmentally respectful microfabrication method that allows the entrapment of biomolecules during the polymer synthesis in a single step. As a proof of concept, biotin was trapped in the polypyrrole matrix and then released in a controlled way through electrical stimulation. It was proven that the polymer keeps its electroactivity after the fabrication and functionalization processes. This biocatalytical-based technique represents a straightforward method for the microfabrication of biological-active conducting polymers, which could be implemented in implantable devices for remotely controlled tissue interactions. Chapter 3, entitled “Azide-PEDOT electrodes. Application to DNA sensors”, describes the fabrication and testing of an electrochemical label-free DNA hybridization sensor, based on novel azidomethyl-modified poly(3,4-ethylenedioxythiophene) electrodes (azide-PEDOT electrodes). These azide-PEDOT electrodes were used as platforms for the immobilization of acetylene-DNA probes, complementary to the “Hepatitis C” virus. The acetylene-DNA probes were covalently grafted to the polymer backbone via the robust “Click” reaction, which a part from being a very selective functionalization method, preserves DNA from denaturation during the synthesis of the polymer. DNA hybridization was detected by Differential Pulse Voltammetry (DPV), where the electrochemical change of the polymer behaviour, produced by the recognition event, was directly evaluated. This fabrication procedure is a powerful tool for the preparation of label-free DNA sensors able to selectively recognize a specific DNA sequence, down to the nanomolar range. Finally, Chapter 4, entitled “Fabrication of polypyrrole single nanowire devices”, discusses the fabrication of polypyrrole at the nanoscale. Two fabrication techniques were investigated here, namely dip pen nanolithography and electrochemical polymerization on template-assisted surfaces. On one hand, the dip pen nanolithography proved to be a simple deposition technique with good control over size and location of the polypyrrole nanowires. On the other hand, the electrochemical polymerization on template-assisted surfaces provided as well nanoscaled polypyrrole, but added the possibility to chemically manipulate the polymer. This chemical manipulation was translated into polymer devices with different electrical properties. By the use of these techniques, the capability of fabricating single nanowire devices (ready to use in different applications) and arrays of ordered nanowires based on conducting polymers is demonstrated. Additionally, two appendixes can be found at the end of the thesis: Appendix A: “Fabrication of azide-PEDOT microwire-based devices” and Appendix B: “Fabrication of nanopatterns by electron-sensitive silanes”. They provide short experimental results obtained during the course of this work, which are first steps for future investigations. A general conclusions section can be found at the end of the thesis, where a summary of the main achievements and contributions of this thesis are listed. / Aunque los polímeros conductores se presentan como una alternativa viable a los materiales convencionalmente usados en aplicaciones biomédicas, las técnicas de fabricación adaptadas a ellos y el aprovechamiento de sus propiedades están lejos de ser completos. Existen importantes limitaciones en la fabricación de micro y nano estructuras basadas en polímeros conductores. Debido a la agresividad de las técnicas tradicionalmente usadas en microelectrónica, se hace necesaria la búsqueda de nuevas estrategias de fabricación adaptadas a polímeros conductores, así como de nuevos procesos que puedan mejorar el rendimiento de los dispositivos diseñados. En esta tesis titulada “Conducting polymers micro and nano electrodes. Application to biomolecule sensing and release”, se han investigado nuevas técnicas de fabricación y de funcionalización de polímeros conductores, poniendo un especial interés en su aplicación biomédica. Una nueva técnica de fabricación de microestructuras de polipirrol por método biocatalítico sobre superficies aislantes ha sido desarrollada con resoluciones comparables a las de la litografía óptica. Dicha técnica es compatible con la incorporación de biomoléculas durante el proceso de síntesis, lo que garantiza su utilización en entornos biológicos. Esto fue demostrado mediante la incorporación de biotina durante el proceso de polimerización y su posterior liberación, mediante estimulo eléctrico. También se ha desarrollado un nuevo sensor de ADN sin marcaje basado en electrodos de azida-PEDOT, para la detección de secuencias basadas en la “Hepatitis C”. Estos electrodos, permiten la directa y covalente funcionalización con secuencias de ADN, modificadas con grupos acetileno, por medio de la química “Click”. La hibridación fue detectada mediante la evaluación de la electroactividad del polímero tras el suceso de reconocimiento. Esta novedosa modalidad de sensores demostró ser selectiva y sensible, siendo capaz de detectar secuencias complementarias en el rango nM, sin necesidad de marcajes, ni complejas técnicas de microfabricación. Finalmente, se estudiaron dos técnicas de fabricación de nanohilos de polímero conductor: nanolitografía de dip-pen y electropolimerización sobre superficies con plantillas. Estos estudios proveen al incompleto campo de la fabricación de nanoestructuras de polímeros conductores de resultados adicionales, que amplían el campo de aplicación de dichos materiales.