Les principales évolutions requises pour répondre aux besoins de la microélectronique visent à intégrer une micro-source d’énergie susceptible de fonctionner à plus bas potentiel que les systèmes actuels. Ainsi, en vue de répondre à cette demande, ce travail de recherche s’est focalisé sur l’étude, principalement par spectroscopie photoélectronique à rayonnement X (XPS), de deux matériaux d’électrode positive fonctionnant à 3 V vs Li+/Li : le spinelle LiMn2O4 et le Nasicon Fe2(MoO4)3. Le bismuth, matériau potentiel d’électrode négative susceptible de remplacer le lithium métallique et de subir le procédé de soudure classiquement utilisé en microélectronique (le solder reflow), est également étudié dans le cadre de cette thèse. Avant de caractériser ces matériaux en systèmes tout-solide, la première étape consiste à en étudier les comportements électrochimiques en électrolytes liquides. A cet effet, des couches minces d’une épaisseur d’environ 500 nm sont préparées par pulvérisation cathodique après une étape d’optimisation des paramètres de dépôt (puissance, pression partielle et totale dans l’enceinte de dépôt, température de recuit, …), puis caractérisées sur les plans structural (DRX), morphologique (SEM) et chimique (XPS, RBS, ICP). L’analyse des échantillons par XPS en fin de décharge et de charge a permis de mieux comprendre et d’expliquer les réactions électrochimiques se produisant au sein des matériaux et aux interfaces électrode/électrolyte dans les batteries au lithium. Une étude comparative avec un cyclage face au sodium a également été menée dans le cas du molybdate de fer et du bismuth, ce qui a permis d’identifier des comportements spécifiques lors de l’insertion/désinsertion des deux alcalins. L’homogénéité de la lithiation/sodation des couches minces a également été étudiée à partir de différentes analyses XPS menées après un procédé de décapage permettant de s’affranchir de la couche de passivation formée à l’interface électrode/électrolyte.Cette étude contribue à une meilleure connaissance des matériaux d’électrodes en cyclage pour micro-batteries au lithium et présente des perspectives très intéressantes d’intégration dans des dispositifs « tout solide ». / The main evolutions required for microelectronic applications aim to integrate an energy microsource operating at lower potential than current systems. Thus, in order to meet this demand, this research work has been focused on the study, mainly by X-ray photoelectron spectroscopy (XPS), of two positive electrode materials operating at 3 V vs Li+/Li: the spinel-type material LiMn2O4 and the Nasicon-type one Fe2(MoO4)3. The bismuth, a potential negative electrode material likely to replace the metallic lithium and to undergo the soldering process conventionally used in microelectronics (the solder reflow), has also been studied in this work. Before studying these materials in all-solid-state systems, the first step consists in investigating their electrochemical behaviors in liquid electrolytes. For this purpose, 500 nm-thick thin films are prepared by magnetron sputtering after a step of deposition parameters optimization (power, partial and total pressures in the sputtering chamber, annealing temperature, etc.). Physicochemical proprieties of the deposited thin films are then investigated by XRD, SEM, XPS, RBS and ICP analyses. The analyses of the electrodes by XPS at the end of discharge and charge has allowed better understanding of the electrochemical reactions occurring within the electrode materials and at the electrode/electrolyte interfaces in lithium cells. A comparative study with cycling against sodium has also been carried out in the case of iron molybdate and bismuth materials. This has allowed identifying specific behaviors of the thin films during the insertion/extraction of the two alkalis. The homogeneity of the thin films lithiation/sodiation has also been studied from various XPS analyses realized after etching process which allows eliminating the passivation layer formed at the electrode/electrolyte interface.This study contributes to a better knowledge of three potential electrode materials candidates for lithium micro-batteries and presents very interesting perspectives of materials integration in all solid state systems.

This work focuses on characterising the chiral and topological nature of magnetic skyrmions in noncentrosymmetric helimagnets. In these materials, the skyrmion lattice phase appears as a long-range-ordered, close-packed lattice of nearly millimetre-level correlation length, while the size of a single skyrmion is 3-100 nm. This is a very challenging range of lengthscales (spanning 5 orders of magnitude from tens of nm to mm) for magnetic characterisation techniques. As a result, only three methods have been proven to be applicable for characterising certain aspects of the magnetic information: neutron diffraction, electron microscopy, and magnetic force microscopy. Nevertheless, none of them reveals the complete information about this fascinating magnetically ordered state. On the largest scale, the skyrmions form a three-dimensional lattice. The lateral structure and the depth profile are of importance for understanding the system. On the mesoscopic scale, the rigid skyrmion lattice can break up into domains, with the domain size about tens to hundreds of micrometers. The information of the domain shape, distribution, and the domain boundary is of great importance for a magnetic system. On the smallest scale, a single skyrmion has an extremely fine structure that is described by the topological winding number, helicity angle, and polarity. These pieces of information reveal the underlying physics of the system, and are currently the focus of spintronics applications. However, so far, there is no experimental technique that allows one to quantitatively study these fine structures. It has to be emphasised that the word 'quantitative' here means that no speculations have to be made and no theoretical modelling is required to assist the data interpretation -- what has been measured must be straightforward, and give a unique and unambiguous answer. Motivated by these questions, we developed soft x-ray scattering techniques that allow us to acquire much deeper microscopic information of the magnetic skyrmions -- reaching far beyond what has been possible so far. We will show that by using only one technique, all the information about the magnetic structure (spanning 5 orders of magnitude in length) can be accurately measured. The thesis is structured as follows: The key development is the Dichroism Extinction Rule, which is summarised in Chapter 6, and quintessentially summarises the thesis. In Chapter 1, the well-established theory for skyrmions is introduced, reconstructing the picture from single skyrmions to the skyrmion crystal. A few comments about the current characterisation techniques will be given. In Chapter 2, we will start with the largest lengthscale, the long-range-ordered skyrmion lattice phase. This is an intensely studied phase, mostly using neutron diffraction, and we will show that this piece of information can be equivalently (or actually even better) obtained using resonant x-ray diffraction. The theoretical foundation of this technique is also given. In Chapter 3, we will demonstrate imaging technique with which we were able to effectively map the skyrmion domains. The measurements also suggest a way to control the formation of skyrmion domains, which might be the key for enabling skyrmion-based device applications. Chapters 4 and 5 present the highlights of this work, in which we will show that using the dichroism extinction rule, the topological winding number and the skyrmion helicity angle can be unambiguously determined. In this sense, this technique is capable of accurately measuring the internal structure of single skyrmions.

Second generation solar cells based on thin film semiconductors emerged as a result of the past ten years of intense research in the thin film preparation technology. Thin film solar cell technology can be cost effective as it uses comparatively cheap materials suitable for solar building integration. Chemical Vapour Deposition (CVD) is a well-known method for the deposition of high quality thin films. This thesis describes the synthesis of novel tin(II)dithiocarbamate [Sn(S2CNEt2)2] and bis(diphenylphosphinediselenoato) tin(II) [Sn(Ph2PSe2)2] and these complexes as single source precursor for the deposition of SnS and SnSe and by using the combination of [Sn(Ph2PSe2)2] with [Cu(acac)2], Cu2SnSe3 thin films were deposited by AACVD. By using suitable combinations of metal complexes ([nBu2Sn(S2CNEt2)2], [Cu(S2CNEt2)2] [Zn(S2CNEt2)2] [Zn(Se2CNEt2)2] [Zn(acac)2], [Sn(OAc)4], [Cu(PPh3){Ph2P(Se)NP(Se)Ph2}] thin films and nanocomposites of CZTS, CFTS, CZTSe, CFTSe, CZFTS, , CZFTSe, CZTSSE, CFTSSe and CZFTSSe were prepared. The effect of precursor concentration and deposition temperature on the structure, morphology and composition of the thin films were studied in detail using by powder X-ray diffraction (p-XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and elemental mapping. This thesis addressing the structural inhomogeneity, control of growth and material characterization is expected to yield closer performance parity between CZTS-Se and CIGS solar cells. A series of systematic experiments were carried out. Through AACVD and simple solvothermal methods CZFTS nanoparticles and thin films were prepared. The simple, potentially, low-cost nature of the CZTS nanoparticles and the enhancement of charge carrier mobility achieved suggest that these nanoparticles have potential in the improvement of OFETs and perhaps other organic electronic devices.

This dissertation considers the genesis and dynamics of interfacial instability in vertical laminar gas-liquid flows, using as a model the two-dimensional channel flow of a thin falling film sheared by counter-current gas. The methodology is linear stability theory by means of Orr-Sommerfeld analysis together with direct numerical simulation of the two-phase flow in the case of nonlinear disturbances. The influence of two main flow parameters on the interfacial dynamics, namely the film thickness and pressure drop applied to drive the gas stream, is investigated. To make contact with existing studies in the literature, the effect of various density and viscosity contrasts as well as surface tension is also examined. Energy budget analyses based on the Orr-Sommerfeld theory reveal various coexisting unstable modes (interfacial, shear, internal) in the case of high density contrasts, which results in mode coalescence and mode competition, but only one dynamically relevant unstable interfacial mode for low and intermediate density contrast. Furthermore, high viscosity contrast and increases in surface tension lead to some amount of mode competition for thin film. A study of absolute and convective instability for low density contrast shows that the system is absolutely unstable for all but two narrow regions of the investigated parameter space. These regions are extended at intermediate density contrast and exhibit only small changes with increased viscosity contrast or surface tension. Direct numerical simulations of the system with low density contrast show that linear theory holds up remarkably well upon the onset of large-amplitude waves as well as the existence of weakly nonlinear waves. For high density contrasts corresponding more closely to an air-water-type system, linear stability theory is also successful at determining the most-dominant features in the interfacial wave dynamics at early-to-intermediate times. Nevertheless, the short waves selected by the linear theory undergo secondary instability and the wave train is no longer regular but rather exhibits chaotic motion. Furthermore, linear stability theory also predicts when the direction of travel of the waves changes - from downwards to upwards. The practical implications of this change in terms of loading and flooding is discussed. The change in direction of the wave propagation is represented graphically for each investigated system in terms of a flow map based on the liquid and gas flow rates and the prediction carries over to the nonlinear regime with only a small deviation. Besides the semi-analytical and numerical analyses, experiments with an practically relevant setup and flow system have been carried out to benchmark and validate the models developed in this work.

It is a well-known fact in the materials science community that the use of low-energy atom impacts during thin film deposition is an effective tool for altering the growth behavior and for increasing the crystallinity of the films. However, the manner in which the incident atoms affect the growth kinetics and surface morphology is quite complicated and still not fully understood. This provides a strong incentive for further investigations of the interaction among incident atoms and surface atoms on the atomic scale. These impact-induced energetic events are non-equilibrium, transient processes which complete in picoseconds. The only accessible technique today which permits direct observation of these events is molecular dynamics (MD) simulations. This thesis deals with MD simulations of low-energy atom impact phenomena on metal surfaces during crystal growth. Platinum is chosen as a model system given that it has seen extended use as a model surface over the past few decades, both in experiments and simulations. In MD, the classical equations of motion are solved numerically for a set of interacting atoms. The atomic interactions are calculated using the embedded atom method (EAM). The EAM is a semi-empirical, pair-functional interatomic potential based on density functional theory. This potential provides a physical picture that includes many-atom effects while retaining computational efficiency needed for larger systems. Single adatoms residing on a surface constitute the smallest possible clusters and are the fundamental components controlling nucleation kinetics. Small two-dimensional clusters on a surface are the result of nucleation and are present during the early stages of growth. These surface structures are chosen as targets in the simulations (papers I and II) to provide further knowledge of the atomistic processes which occur during deposition, to investigate at which impact energies the different kinetic pathways open up, and how they may affect growth behavior. Some of the events observed are adatom scattering, dimer formation, cluster disruption, formation of three-dimensional clusters, and residual vacancy formation. Given the knowledge obtained, papers III and IV deal with growth of several layers with the aim to study the underlying mechanisms responsible for altering growth behavior and how the overall intra- and interlayer atomic migration can be controlled by low-energy atom impacts. / <p>On the day of the defence date the status of article II was Accepted.</p>

Face à la volonté d’intégrer une quantité toujours plus importante de nouveaux services au sein des terminaux mobiles de nouvelle génération et afin de répondre à leurs contraintes d’encombrement, des nouveaux concepts d’antennes intelligentes font l’objet de nombreuses recherches. Parmi les solutions proposées dans la littérature, la technique consistant à charger l’antenne par un matériau aux propriétés commandables apparaît particulièrement intéressante puisque elle cumule les effets de miniaturisation et d’agilité. Le travail de cette thèse concerne l’intégration des films minces La-Ti-O-N et BST dans des antennes miniatures et agiles en fréquence. Pour cela, une étude systématique des propriétés diélectriques (constante, tangente de pertes et accordabilité) des films La-Ti-O-N a été réalisée en basses et hautes fréquences. Ces propriétés sont fonction des caractéristiques structurales des films, elles-mêmes issues de la nature du substrat utilisé et des conditions de dépôt. En parallèle, une étude sur l’intégration de ces matériaux dans des structures rayonnantes pour atteindre l’agilité souhaitée a été menée. De premiers démonstrateurs d’antennes miniatures et reconfigurables à base des films minces La-Ti-O-N et BST ont été réalisés et caractérisés. / Given the desire to integrate a large number of new services in latest generation of hand held devices and in order to meet their dimensional constraints, new concepts of smart antennas are considered to be the subject of many researches. Among several solutions mentioned in the bibliography, the technique of loading the antenna with tunable material is particularly interesting because it combines the effects of miniaturization and tunability. The studies in this thesis focus on the integration of La-Ti-O-N and BST thin films in antenna conception for miniaturization and agility in frequency. A study of dielectric properties (permittivity, loss tangent and tunability) of La-Ti-ON thin films was realized. These properties are found to be depending on the structural characteristics of the thin films, which derived from the nature of the substrate and the deposition conditions. In the mean time, another study for the integration of these materials in radiating structures to achieve agility in frequency was carried out. Demonstrations of miniaturized and reconfigurable antennas based on La-Ti-ON and BST thin films were fabricated and characterized.

The buffer layer is a crucial component in thin film solar cells. Defects at the interface between absorber and buffer layer lead to high recombination rate and the band structure at the interface highly affects the performance of the solar cell. In this thesis a method to synthesize thin films containing cadmium, zinc and sulfur, CdZnS, by chemical bath deposition has been developed and evaluated. A higher current from the device is expected when replacing the common buffer layer cadmium sulfide, CdS, with the more transparent CdZnS. It is also possible that the alternative buffer provides a more favorable energy band alignment at the interface with the absorber Copper-Zinc-Tin-Sulfide (CZTS). The deposition process was developed by studying depositions on glass. Increasing [Zn2+]/[Cd2+] initially led to films with higher band gap (Eg). By varying deposition time the time before colloidal growth became dominant was observed. Addition of triethanolamine showed that triethanolamine binds stronger to zinc ions than to cadmium ions. Two recipes that led to Eg=2.63 eV were evaluated as buffer layer in Copper-Indium-Gallium-Selenide (CIGSe) and CZTS solar cells. The short circuit current of the devices increased in general with the CdZnS buffers compared to CdS. The best CZTS cell with a CdZnS buffer layer had 7.7 % efficiency compared to the 7.5 % reference. For future research it is recommended that the effect of thickness variation and deposition temperature is evaluated and that additional material characterization is performed in order to further understand and develop the deposition method.

Nas últimas décadas, o interesse na eletrônica flexível tem aumentado. Sistemas que apresentam benefícios, tais como: baixo custo, melhor desempenho, transparência, confiabilidade e melhores credenciais ecológicas, estão sendo extensivamente pesquisados por vários grupos. Os transistores de filmes-finos possuem potencial para alcançarem essas características. Dispositivos baseados em óxido de zinco (ZnO) tem atraído pesquisadores devido as suas propriedades elétricas, sensoriais e ópticas. Neste trabalho, nanopartículas de ZnO foram utilizadas como semicondutor ativo e cross-linked PVP (polivinilfenol) e PECVD-SiO2 (plasma enhanced chemical vapor deposition silicon dioxide) como dielétricos de porta para integrar transistores de filmes-finos. Este processo de integração tem por objetivo os pré-requisitos de baixo custo e baixa temperatura (<200°C). Por esta razão, a utilização de técnicas de integração simples, como o spin-coating ou a técnica de sidewall-etchback, foram utilizadas. Infelizmente, existem problemas relacionados à confiabilidade em dispositivos baseados em ZnO, entre eles a degradação no tempo ou a histerese. Após uma investigação experimental da histerese na característica de transferência, um modelo qualitativo para o comportamento observado é proposto. Observou-se que a direção da histerese é afetada pela variação da temperatura quando o dielétrico polimérico é usado. Baseando-se na caracterização dos transistores, a polarização do PVP, as armadilhas na superfície das nanopartículas e na interface com o dielétrico, bem como a liberação de moléculas de oxigênio da superfície das nanopartículas foram atribuídas como as principais causas da histerese. Além disso, uma flutuação discreta da corrente é observada em testes de estresse devido à captura e liberação de portadores em determinados caminhos de corrente no transistor, semelhante a random telegraph signal (RTS), relatado em MOSFET nanométricos. Este resultado suporta o hipotético mecanismo de transporte de elétrons (caminhos de percolação) em filmes compostos por ZnO nanoparticulado. / During the last decades, the interest in flexible electronics has arisen. Systems that present benefits such as low cost, improved performance, transparency, reliability and better environmental credential are being extensively researched by several groups. Thin-film transistors (TFT) have good potential concerning these technologies. Therefore, zinc oxide (ZnO) based devices have been attracting researchers for its electrical, sensory and optical properties. In this work, ZnO nanoparticles were used to integrate thin-film transistors, in which cross-linked PVP (Poly(4-vinylphenol)) and PECVD-SiO2 (plasma enhanced chemical vapor deposition silicon dioxide) were used as gate dielectric layer. The complete integration process targets low cost and low temperature requirements (< 200°C). For this reason, simple process techniques as spin-coating or sidewall-etchback were used. Unfortunately, there are different reliability concerns in ZnO devices, among them aging or hysteresis. An experimental investigation of the hysteresis in the transfer characteristic is performed, and a qualitative model for the observed behavior is proposed. It was observed that the hysteresis direction is affected by temperature variation when the polymeric dielectric is used. The PVP bulk polarization, the traps in nanoparticles and at the polymeric dielectric interface, as well as the desorption of oxygen molecules in the surface of the nanoparticles, were attributed as the main cause of the hysteretic behavior. Moreover, capture and release of charge carriers by traps at determined current paths in the transistor lead to discrete current fluctuations in stress tests, similar to random telegraph signal (RTS) reported in nanoscale MOSFET. This result supports the hypothesis of charge transport mechanism (percolation paths) in nanoparticulate ZnO.

Nas últimas décadas, sistemas de suprimento de energia que utilizam recursos renováveis têm sido estudados e empregados como opção para o fornecimento de energia elétrica. Devido aos avanços da tecnologia fotovoltaica, associada à diminuição de custos e maior conhecimento de seu desempenho, os sistemas fotovoltaicos apresentam-se como uma opção tecnicamente promissora. Neste contexto, a energia solar fotovoltaica, que, além de gerar eletricidade de forma distribuída também vem ganhando cada vez mais espaço no mercado mundial. Esta tecnologia evita as emissões de gases poluentes e é uma fonte alternativa que diversifica a matriz energética. Para complemento da energia hidrelétrica é necessária uma fonte energética com várias características ecologicamente corretas, a energia solar fotovoltaica é uma dessas fontes, pois é limpa (não poluente), inesgotável, silenciosa, estática, distributiva, simples em sua operação, possui características modulares podendo-se integrar as edificações. Para viabilizar sua implantação nas edificações, vários países, inclusive o Brasil, também buscam soluções para o futuro, elaborando estudos para avaliar a eficácia dessa tecnologia. Adicionalmente, como a energia é cada vez mais necessária para o desenvolvimento humano, utilizar a fonte de geração próxima ao ponto de consumo é uma maneira eficaz de reduzir as perdas por transmissão e distribuição. Esta dissertação tem por objetivo apresentar os conceitos, aspectos e aplicações das células solares de filmes finos na inserção como gerador fotovoltaico de energia elétrica integrada a estrutura das edificações. O foco principal do tema da dissertação é o estudo de área disponível na edificação, estimando o potencial fotovoltaico de geração existente no envoltório. Através desta análise, pode-se quantificar a contribuição energética de uma unidade geradora fotovoltaica para a redução de consumo energético na rede em que a edificação estiver conectada. / In recent decades, energy supply systems that use renewable resources have been studied and used as an option for the supply of electricity. Due to advances in photovoltaic technology, coupled with lower costs and greater knowledge of its performance, photovoltaic systems are presented as an option technically promising. In this context, photovoltaic solar energy, this, besides generating electricity in distributed also gaining more and more space in the world market. This technology avoids the emissions of greenhouse gases and is an alternative source to diversify the energy matrix. To complement the hydropower energy supply is needed with various features eco-friendly, photovoltaic solar energy is one of those sources, because it is clean (clean) endless, silent, static, distributive, simple in its operation, has modular features can to integrate the buildings. To enable its deployment in buildings, several countries, including Brazil, also look for solutions for the future, preparing studies to evaluate the effectiveness of this technology. Additionally, energy is increasingly necessary for human development, using the power generation near the point of consumption is an effective way to reduce transmission and distribution losses. This paper aims to present the concepts, issues and applications of thin film solar cells in photovoltaic generator insertion as power integrated structure of buildings. The main focus of the dissertation topic is the study of the available area in the building, estimating the potential of photovoltaic generation in existing wrap. Through this analysis, one can quantify the energy contribution of a photovoltaic generating unit to reduce energy consumption in the network in which the building is connected.

This thesis presents the development of all-inkjet-printed low-voltage organic thin-film transistors. Organic thin-film transistors (OTFTs), taking advantage of low-temperature printability, mechanical flexibility, and multi-functionality, are promising for a wide range of emerging applications such as wearable electronics. Printed OTFTs provide great benefits in fabrication cost reduction, but they need a very high operating voltage and exhibit severe instability during storage and operation in ambient environment. In this study, all-inkjet-printed OTFTs with a low operating voltage of less than 3 V are demonstrated through reducing trap density in the fabricated devices. The transistors use 6,13-bis(triisopropylsilylethynyl)pentacene as the semiconductor, poly(4-vinylphenol) as the dielectric, silver as the electrodes, and CYTOP as the encapsulation. Several aspects of physical and chemical properties of polymer dielectrics are studied to achieve this goal, including cross-linking, wetting, and moisture affinity. Through the careful selection of device architecture and control of the inkjet-printing processes, the semiconductor-dielectric interface trap density of the fabricated OTFTs is significantly reduced. The applicability of this approach to different materials is also investigated and confirmed, including polyvinyl cinnamate as the dielectric, 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene as the semiconductor, and anisole as the solvent for semiconductor inks. Based on the investigation of different materials, the characteristics and parameters of all-inkjet-printed OTFTs are optimised, demonstrating an ultra-steep subthreshold of 60.2 mV/decade approaching the theoretical limit and a low operating voltage of 1 V. In order to explore their feasibility in real-world applications, the stability of all-inkjet-printed OTFTs is investigated and the factors of instability are analysed. Based on these findings, the stability of the fabricated device is improved, such that the threshold voltage shift is less than 0.1 V in ambient environment storage for 3 months and operation for 1 hour. The electrical characteristics of OTFTs in the subthreshold regime are studied for analogue circuit design. Based on the developed low-voltage stable transistors, an ultra-low-power (< 1 nW) high-gain (> 200 V/V) amplifier is presented and utilised to detect electrophysiological signals from the human body.