L’objectif de cette thèse était de synthétiser des multicouches à base de couches ferromagnétiques GeMn qui sont empilées et séparées par des couches de Ge en utilisant la technique d'épitaxie par jets moléculaires.Outre de nombreuses applications en spintronique issues de cette structure de matériaux, la réalisation de capteurs biochimiques dédiés à la détection moléculaire est l’idée directrice de ce travail. Un tel dispositif présenterait les atouts que ses matériaux constituants apportent : haute sensibilité, sélectivité et compatibilité parfaite avec la technologie de Si-Ge. Dans la première partie de ce manuscrit sont présentés les résultats obtenus de la croissance d’hétérostructures Mn5Ge3, Mn5Ge3Cx sur Ge(111) puis la reprise d’épitaxie de la barrière de Ge sur Mn5Ge3, la première étape avant la croissance de la deuxième couche ferromagnétique. Nous avons également analysé les propriétés structurales et magnétiques de ces couches minces ainsi que les dificultés dues à la croissance de la couche de Ge, notamment la diffusion et la ségrégation. Deux approches utilisant le carbone ont été proposées pour réduire la ségrégation : barrière de diffusion en carbone et remplissage des sites interstitiels du réseau Mn5Ge3 par du carbone. Le second axe alternatif pour la synthèse est consacré à la croissance de la structure colonnaire empilée Ge1-xMnx. Les conditions pour obtenir la structure colonnaire ont été déterminées. Les propriétés structurales et mesures magnétiques ont montré que cette phase était particulièrement intéressant dans la famille des semiconducteurs ferromagnétiques dilués à base de Ge-Mn pour les applications en spintronique et croissance de multicouches. La reprise d’épitaxie de plusieurs couches ferromagnétiques séparées par Ge a été effectuée et l’étude du couplage magnétique a été également menée. Enfin, nous présentons les premiers résultats sur le greffage de porphyrines et de protéines sur diverses surfaces hydrophiles et hydrophobes (Si, Ge), permettant d’accéder aux études de la faisabilité des capteurs Ge/GeMn. L’ensemble de ce travail indique que les multicouches de Ge/GeMn apparaissent comme des candidats à fort potentiel pour la spintronique, notamment pour capteurs bio-chimiques dans les semi-conducteurs du groupe IV. / The objective of this thesis is to synthetize the multilayers based on the sandwiched structure of GeMn ferromagnetic layers by mean of Molecular Beam Epitaxy on Ge substrate. Applications in spintronic field from this study are potential such as structures of spin valves, nanoscale sensors devoted to the detection of biochemical molecules. We actually focus on the biochemical sensors based on GMR (or TMR) phenomenon in stacking layered structure. These devices offer many advantages that the constituent materials may provide : high sensibility, selectivity, and especially, compatibility with Si-Ge technology. The first part of this manuscript presents the results obtained of heterostructure growth of Mn5Ge3, Mn5Ge3Cx on Ge(111), then Ge overgrowth on Mn5Ge3, the first step to study multilayers growth. Also, we have discussed about the structural and magnetic properties of these thin films as well as the problems due to the growth of multilayers, especially the diffusion and segregation. The approaches to reduce the diffusion were proposed by introducing carbon atoms as diffusion barrier or by fulfilling insterstial sites of Mn5Ge3 lattice by carbon atoms. The second axis of materials synthesis is devoted to the growth of multilayers Ge1-xMnx nanocolumn structure. The growth condition of Ge1-xMnx nanocolumns has been determined. We have studied structural and magnetic properties of this phase which are of particular interest to spintronic applications and multilayers growth. The Ge/Ge1-xMnx nanocolumns multilayers have been done and the interlayer exchange coupling between ferromagnetic layers has been studied. Finally, we have presented the preliminary results of porphyrin molecules and protein grafting on hydrophilic and hydrophobic surfaces (Si and Ge). This allows accessing to study the feasibility of Ge/GeMn-based sensors. This work indicates that the Ge/GeMn mutilayers appear to be a potential candidate for spintronics and biochemical sensors in the group IV semi-conductors.

Le développement des structures de grains se formant durant les procédés de soudage par fusion a un large impact sur les propriétés et la résistance mécaniques des assemblages. Des défauts, tels que la fissuration à chaud, sont aussi liés à la texturation de grains propre à l'étape de solidification. La simulation directe du développement tri-dimensionnelle (3D) des structures de grains dans ces procédés, à l'échelle industrielle, est rarement proposée. Dans ce travail, une modélisation couplée 3D Automate Cellulaire (CA) – Eléments Finis (FE) est proposée pour prédire la formation des structures de grains dans les procédés de soudage multipasses GTAW (Gas Metal Arc Welding) et GMAW (Gas Metal Arc Welding). A l'échelle macroscopique, la modélisation FE permet la résolution des équations de conservation de la masse, de l'énergie et de la quantité de mouvement pour l'ensemble du domaine en s'appuyant sur un maillage adaptatif. Pour le procédé GMAW avec apport de matière, le modèle FE est enrichi et développé dans une approche level set (LS) afin de modéliser l'évolution de l'interface métal / air due au développement du cordon de soudure. Le domaine FE contient ainsi la pièce étudiée et l'air environnant dans lequel le cordon se développe. Les calculs FE sont couplés avec l'approche CA utilisée pour modéliser le développement de la structure de grains. Un maillage fixe (‘maillage CA') est superposé au maillage adaptatif FE (‘maillage FE'). Les champs macroscopiques propres au maillage FE sont ainsi interpolés entre le maillage adaptatif FE et le maillage fixe CA. Une nouvelle stratégie d'allocation / désallocation de la grille de cellules CA est ensuite utilisée basée sur l'allocation / désallocation des éléments du maillage CA. La grille CA est constituée d'un ensemble régulier de cellules cubiques superposées au domaine soudée. A l'échelle micro-, la grille est utilisée afin de simuler les étapes de fusion et solidification, à la frontière entre le domaine pâteux et le bain liquide, durant le processus de soudage. Les évolutions de températures des cellules sont définies par interpolation du maillage CA. Un couplage du modèle avec les chemins de solidification et les évolutions enthalpiques tabulés est aussi implémenté, permettant de suivre la thermique et les évolutions de fractions de phase propre à l'évolution du procédé. Avec de réduire les temps de calcul et la quantité de mémoire informatique nécessaire à ces simulations, une optimisation des maillages FE/CA et des tailles de cellules CA est proposée pour les deux approches FE et CA. La modélisation 3D proposée est appliquée à la simulation de la formation des structures de solidification formées durant le soudage GTAW et GMAW multipasses de pièces d'acier inoxydables de nuances UR 2202. Dans le procédé GTAW, l'influence de l'évolution des structures de grains selon les paramètres procédés est étudiée. L'orientation normale des grains avec l'augmentation de la vitesse de soudage est montrée. Dans le procédé GMAW, la modélisation permet de simuler la refusion et la croissance des grains des couches successives. De manière générale, les structures de grains prédites montrent qualitativement les évolutions attendues présentées dans la littérature. / Grain structure formation during fusion welding processes has a significant impact on the mechanical strength of the joint. Defects such as hot cracking are also linked to the crystallographic texture formed during the solidification step. Direct simulation of three-dimensional (3D) grain structure at industrial scale for welding processes is rarely modeled. In this work, a 3D coupled Cellular Automaton (CA) – Finite Element (FE) model is proposed to predict the grain structure formation during multiple passes Gas Tungsten Arc Welding (GTAW) and Gas Metal Arc Welding (GMAW). At the macroscopic scale, the FE model solves the mass, energy and momentum conservation equations for the whole system based on an adaptive mesh. For GMAW with metal addition, the FE model is enriched and established in a level set (LS) approach in order to model the evolution of the metal/air interface due to the weld bead development. The FE domain then contains the workpiece and the surrounding air where the weld bead forms. FE computations are coupled with the CA approach used to model the grain structure evolution. A fixed mesh, referred to as CA mesh, is superimposed to the adaptive FE mesh. FE fields are interpolated between the adaptive FE mesh and the fixed CA mesh. A new dynamic allocation/deallocation strategy of a CA grid of cells is then used based on the dynamic activation/deactivation of the elements of the CA mesh. The CA grid is made of a regular lattice of cubic cells superimposed onto the welded domain. At the micro scale, this grid is used in order to simulate the melting and solidification steps at the boundaries between the mushy domain and the liquid pool during the welding process. The temperature evolutions of the cells are computed by interpolation from the CA mesh. Coupling with tabulated transformation paths and phase enthalpy is also implemented, which permits to track the phase amount and latent heat release during the process. In order to master the resolution time and memory cost of the simulations, a management of the FE/CA mesh dimensions and CA cell size is considered for both FE and CA models. The 3D CAFE model is applied to simulate the formation of solidification structures during multiple passes GTAW and GMAW processes on a duplex stainless steel UR 2202. In GTAW, the evolution of the grain structures with respect to the welding process parameters is considered. The normal orientation of the grains with the increase of the heat source velocity is shown. In GMAW, the model is shown to compute the remelting and growth of successively deposited layers. Overall, the predicted structures qualitatively reveal the expected evolutions presented in the literature.

Este trabalho apresenta o estudo do comportamento da resistência série de fonte e dreno em transistores SOI FinFET de porta tripla e com canal tensionado. Nos dispositivos SOI FinFETs há um aumento da resistência série de fonte e dreno devido ao estreitamento dessas regiões, sendo esse parâmetro considerado como uma das limitações quanto à introdução desses dispositivos em tecnologias futuras. O uso de tensão mecânica no canal dos dispositivos surge como alternativa para aumentar a condução de corrente através do aumento da mobilidade dos portadores do canal, reduzindo assim, a resistência total dos transistores e, conseqüentemente, a resistência série de fonte e dreno. Inicialmente, foi feito o estudo de alguns métodos de extração da resistência série de fonte e dreno existentes na literatura, com o objetivo de se obter o mais adequado para aplicação e análise posterior. Esse trabalho foi realizado baseado em resultados experimentais e em simulações numéricas que possibilitaram o entendimento físico do fenômeno estudado. A resistência série de fonte e dreno foi explorada em diferentes tecnologias, como transistores SOI FinFETs de porta tripla convencionais e sob influência de tensionamento uniaxial e biaxial. O uso do crescimento seletivo epitaxial (SEG) nas regiões de fonte e dreno altamente dopadas das diferentes tecnologias também foi analisado, pois com essa técnica, a resistência série de fonte e dreno é reduzida substancialmente não comprometendo a condução de corrente e a transcondutância. Os resultados obtidos das diferentes tecnologias com e sem o uso de SEG foram analisados e comparados mostrando que em transistores SOI FinFETs de porta tripla, com crescimento seletivo epitaxial, apresentam o menor valor da resistência série de fonte e dreno mesmo para aqueles sem tensão mecânica na região do canal. / This work presents the study of the source and drain series resistance behavior in standard and strained SOI FinFETs triple gate transistors. In SOI FinFETs transistors there is an increase of the source and drain series resistance due to the narrow of these regions, being this parameter a key limiting factor to the next generations. The use of strained transistors is one of the potential technologies to the next generation high performance because it increase the drive current through an enhance in the carrier mobility, decreasing the transistors total resistance and, therefore, the source and drain series resistance. Initially, a study of some series resistance extraction methods, present in the literature was done, in order to obtain the most appropriate for applications and analysis subsequent. This work was done based on experimental results and numerical simulations, enabling the physical understanding of the phenomenon studied. The series resistance was explored in different technologies, as standard SOI FinFETs triple gates and with uniaxial and biaxial strain. The use of selective epitaxial growth (SEG) in the source and drain regions, with high doping levels, was also studied in the different technologies, because with the use of this technique, the series resistance decreases substantially without compromising the drive current and transconductance. The obtained results from the different technologies with and without the use of SEG were analyzed and compared showing that, SOI FinFETs triple gate transistors with SEG present the lower values of series resistance even for standard devices if compared with strained ones without the use of SEG.

Este trabalho apresenta o estudo da influência do tensionamento mecânico (strain) no efeito de abaixamento de barreira induzido pelo dreno (DIBL) em dispositivos SOI FinFETs de porta tripla com e sem crescimento seletivo epitaxial. Também é analisada a influência do uso de crescimento seletivo epitaxial nesses dispositivos em relação ao efeito de canal curto mencionado. O uso de transistores verticais de múltiplas portas tem permitido a continuidade do escalamento dos dispositivos, apresentando melhora nos níveis de corrente bem como a supressão dos efeitos de canal curto. No entanto, ao reduzir a largura do canal, aumenta-se a resistência total do transistor, diminuindo seu desempenho. A fim de melhorar essa característica, as técnicas de tensionamento mecânico e crescimento de fonte e dreno tem sido empregadas. No primeiro caso, ao se deformar mecanicamente a estrutura do canal, altera-se o arranjo das camadas eletrônicas que ocasiona o aumento da mobilidade dos portadores. Conseqüentemente, a corrente aumenta tal como a transcondutância do dispositivo. A técnica de crescimento de fonte e dreno chamada de crescimento seletivo epitaxial (SEG) tem como finalidade reduzir ainda mais a resistência elétrica total da estrutura, uma vez que a área dessas regiões aumenta, possibilitando o aumento das áreas de contato, que são responsáveis pela maior parcela da resistência total. Esse trabalho baseia-se em resultados experimentais e simulações numéricas tridimensionais que analisam o comportamento dos transistores com as tecnologias acima apresentadas em função do efeito de DIBL. / This work presents a study about the influence of strain in the drain induced barrier lowering effect (DIBL) in triple gate SOI FinFETs. Also it is analyzed the selective epitaxial growth used in that structures, comparing their behavior in relation to DIBL effect. Using the vertical multi-gate devices become possible the downscale whereas they present higher current level and suppressed short channel effects. However, reducing the channel width, the transistors total resistance increases and consequently its performance decreases. In order to improve this feature, the strained technology and the Source/Drains growth technique has been employed. In the first case, the mechanical deformation causes a change in the electron shell, which improves the carrier mobility. Consequently, the current level and the transconductance also improve. The selective epitaxial growth technique aims to reduce the devices total resistance since these regions areas increase, allowing large contacts which are responsible for the main parcel of the total resistance. This work is based on experimental results and tridimensional simulations that analyze the transistor behavior using the technologies above presented as a function of DIBL effect.

Este trabalho apresenta o estudo do comportamento da resistência série de fonte e dreno em transistores SOI FinFET de porta tripla e com canal tensionado. Nos dispositivos SOI FinFETs há um aumento da resistência série de fonte e dreno devido ao estreitamento dessas regiões, sendo esse parâmetro considerado como uma das limitações quanto à introdução desses dispositivos em tecnologias futuras. O uso de tensão mecânica no canal dos dispositivos surge como alternativa para aumentar a condução de corrente através do aumento da mobilidade dos portadores do canal, reduzindo assim, a resistência total dos transistores e, conseqüentemente, a resistência série de fonte e dreno. Inicialmente, foi feito o estudo de alguns métodos de extração da resistência série de fonte e dreno existentes na literatura, com o objetivo de se obter o mais adequado para aplicação e análise posterior. Esse trabalho foi realizado baseado em resultados experimentais e em simulações numéricas que possibilitaram o entendimento físico do fenômeno estudado. A resistência série de fonte e dreno foi explorada em diferentes tecnologias, como transistores SOI FinFETs de porta tripla convencionais e sob influência de tensionamento uniaxial e biaxial. O uso do crescimento seletivo epitaxial (SEG) nas regiões de fonte e dreno altamente dopadas das diferentes tecnologias também foi analisado, pois com essa técnica, a resistência série de fonte e dreno é reduzida substancialmente não comprometendo a condução de corrente e a transcondutância. Os resultados obtidos das diferentes tecnologias com e sem o uso de SEG foram analisados e comparados mostrando que em transistores SOI FinFETs de porta tripla, com crescimento seletivo epitaxial, apresentam o menor valor da resistência série de fonte e dreno mesmo para aqueles sem tensão mecânica na região do canal. / This work presents the study of the source and drain series resistance behavior in standard and strained SOI FinFETs triple gate transistors. In SOI FinFETs transistors there is an increase of the source and drain series resistance due to the narrow of these regions, being this parameter a key limiting factor to the next generations. The use of strained transistors is one of the potential technologies to the next generation high performance because it increase the drive current through an enhance in the carrier mobility, decreasing the transistors total resistance and, therefore, the source and drain series resistance. Initially, a study of some series resistance extraction methods, present in the literature was done, in order to obtain the most appropriate for applications and analysis subsequent. This work was done based on experimental results and numerical simulations, enabling the physical understanding of the phenomenon studied. The series resistance was explored in different technologies, as standard SOI FinFETs triple gates and with uniaxial and biaxial strain. The use of selective epitaxial growth (SEG) in the source and drain regions, with high doping levels, was also studied in the different technologies, because with the use of this technique, the series resistance decreases substantially without compromising the drive current and transconductance. The obtained results from the different technologies with and without the use of SEG were analyzed and compared showing that, SOI FinFETs triple gate transistors with SEG present the lower values of series resistance even for standard devices if compared with strained ones without the use of SEG.

Properties of magnetic thin film devices cannot be understood without detailed knowledge of their structure. For this purpose, a variety of thin film and multilayer systems have been studied. Both reciprocal space (low energy electron diffraction, reflection high energy electron diffraction, X-ray diffraction and reflectometry) and direct space (transmission electron microscopy) as well as Rutherford backscattering spectrometry have been applied. To gain understanding of an oxidation procedure for the growth of magnetite layers, thermal stability of iron layers on molybdenum seed layers has been investigated. Following the mosaicity and the out-of-plane coherence length over different ratios between the constituting layers allowed a deeper understanding of the limits of metallic superlattices. This, together with an approach to use hydrogen in the process gas during magnetron sputter epitaxy, opens routes for the growth of metallic superlattices of superior quality. A non-isostructural multilayer/superlattice system, Fe/MgO, has been investigated. In turn, this gave more understanding how superlattice diffraction patterns are suppressed by strain fields. As an alternative route to single-crystalline superlattices, amorphous multilayers present interesting opportunities. In this context, crystallization effects of iron/zirconium layers on alumiunium oxide were studied. Understanding these effects enables significant improvement in the quality of amorphous multilayers, and allows avoiding these, growing truly amorphous layers. Both the substantial improvement in quality of metallic superlattices, approaching true single-crystallinity, as well as the improvements in the growth of amorphous multilayers give rise to opportunities in the field of magnetic coupling and superconducting spin valves.

Efficiency droop is a critical issue for the Group III-nitride based light-emitting diodes (LEDs) to be competitive in the general lighting application. Carrier spill-over have been suggested as an origin of the efficiency droop, and an InAlN electron-blocking layer (EBL) is suggested as a replacement of the conventional AlGaN EBL for improved performance of LED. Optimum growth condition of InAlN layer was developed, and high quality InAlN layer was grown by using metalorganic chemical vapor deposition (MOCVD). A LED structure employing an InAlN EBL was grown and its efficiency droop performance was compared with a LED with an AlGaN EBL. Characterization results suggested that the InAlN EBL delivers more effective electron blocking over AlGaN EBL. Hole-injection performance of the InAlN EBL was examined by growing and testing a series of LEDs with different InAlN EBL thickness. Analysis results by using extended quantum efficiency model shows that further improvement in the performance of LED requires better hole-injection performance of the InAlN EBL. Advanced EBL structures such as strain-engineered InAlN EBL and compositionally-graded InAlN EBLs for the delivery of higher hole-injection efficiency were also grown and tested.

Silicon carbide (SiC) has higher breakdown field strength than silicon (Si), which enables thinner and more highly doped drift layers compared to Si. Consequently, the power losses can be reduced compared to Si-based power conversion systems. Moreover, SiC allows the power conversion systems to operate at high temperatures up to 250 oC. With such expectations, SiC is considered as the material of choice for modern power semiconductor devices for high efficiencies, high temperatures, and high power densities. Besides the material benefits, the typeof the power device also plays an important role in determining the system performance. Compared to the SiC metal-oxide semiconductor field-effect transistor (MOSFET) and bipolar junction transistor (BJT), the SiC junction field-effect transistor (JFET) is a very promising power switch, being a voltage-controlled device without oxide reliability issues. Its channel iscontrolled by a p-n junction. However, the present JFETs are not optimized yet with regard to on-state resistance, controllability of threshold voltage, and Miller capacitance. In this thesis, the state-of-the-art SiC JFETs are introduced with buried-grid (BG) technology.The buried grid is formed in the channel through epitaxial growth and etching processes. Through simulation studies, the new concepts of normally-on and -off BG JFETs with 1200 V blocking capability are investigated in terms of static and dynamic characteristics. Additionally, two case studies are performed in order to evaluate total losses on the system level. These investigations can be provided to a power circuit designer for fully exploiting the benefit of power devices. Additionally, they can serve as accurate device models and guidelines considering the switching performance. The BG concept utilized for JFETs has been also used for further development of SiC junctionbarrier Schottky (JBS) diodes. Especially, this design concept gives a great impact on high temperature operation due to efficient shielding of the Schottky interface from high electric fields. By means of simulations, the device structures with implanted and epitaxial p-grid formations, respectively, are compared regarding threshold voltage, blocking voltage, and maximum electric field at the Schottky interface. The results show that the device with an epitaxial grid can be more efficient at high temperatures than that with an implanted grid. To realize this concept, the device with implanted grid was optimized using simulations, fabricated and verified through experiments. The BG JBS diode clearly shows that the leakage current is four orders of magnitude lower than that of a pure Schottky diode at an operation temperature of 175 oC and 2 to 3 orders of magnitude lower than that of commercial JBS diodes. Finally, commercialized vertical trench JFETs are evaluated both in simulations andexperiments, while it is important to determine the limits of the existing JFETs and study their performance in parallel operation. Especially, the influence of uncertain parameters of the devices and the circuit configuration on the switching performance are determined through simulations and experiments. / Kiselkarbid (SiC) har en högre genombrottsfältstyrka än kisel, vilket möjliggör tunnare och mer högdopade driftområden jämfört med kisel. Följaktligen kan förlusterna reduceras jämfört med kiselbaserade omvandlarsystem. Dessutom tillåter SiC drift vid temperatures upp till 250 oC. Dessa utsikter gör att SiC anses vara halvledarmaterialet för moderna effekthalvledarkomponenter för hög verkningsgrad, hög temperature och hög kompakthet. Förutom materialegenskaperna är också komponenttypen avgörande för att bestämma systemets prestanda. Jämfört med SiC MOSFETen och bipolärtransistorn i SiC är SiC JFETen en mycket lovande component, eftersom den är spänningsstyrd och saknar tillförlitlighetsproblem med oxidskikt. Dess kanal styrs an en PNövergång. Emellertid är dagens JFETar inte optimerade med hänseende till on-state resistans, styrbarhet av tröskelspänning och Miller-kapacitans. I denna avhandling introduceras state-of-the-art SiC JFETar med buried-grid (BG) teknologi. Denna åstadkommes genom epitaxi och etsningsprocesser. Medelst simulering undersöks nya concept för normally-on och normally-off BG JFETar med blockspänningen 1200 V. Såvä statiska som dynamiska egenskper undersöks. Dessutom görs två fallstudier vad avser totalförluster på systemnivå. Dessa undersökningar kan vara värdefulla för en konstruktör för att till fullo utnyttja fördelarna av komponenterna. Dessutom kan resultaten från undersökningarna användas som komponentmodeller och anvisningar vad gäller switch-egenskaper. BG konceptet som använts för JFETar har också använts för vidareutveckling av så kallade JBS-dioder. Speciellt ger denna konstruktion stora fördelar vid höga temperature genom en effektiv skärmning av Schottkyövergången mot höga elektriska fält. Genom simuleringar har komponentstrukturer med implanterade och epitaxiella grids jämförst med hänseende till tröskelspänning, genombrottspänning och maximalt elektriskt fält vid Schottky-övergången. Resultaten visar att den epitaxiella varianten kan vara mer effektiv än den implanterade vid höga temperaturer. För att realisera detta concept optimerades en komponent med implanterat grid med hjälp av simuleringar. Denna component tillverkades sedan och verifierades genom experiment. BG JBS-dioden visar tydligt att läckströmmen är fyra storleksordningar lägre än för en ren Schottky-diod vid 175 oC, och två till tre storleksordningar lägre än för kommersiella JBS-dioder. Slutligen utvärderas kommersiella vertical trench-JFETar bade genom simuleringar och experiment, eftersom det är viktigt att bestämma gränserna för existerande JFETar och studera parallelkoppling. Speciellt studeras inverkan av obestämda parametrar och kretsens konfigurering på switchegenskaperna. Arbetet utförs bade genom simuleringar och experiment. / <p>QC 20150915</p>

Oxide ultra-thin film surfaces have properties and structures that are significantly different from the terminations of the corresponding bulk crystals. For example, surface structures of epitaxial ultra-thin oxide films are highly influenced by the crystallinity and electronegativity of the metal substrates they grown on. Some enhanced properties of the novel reconstructions are related to catalysis, sensing and microelectronics, which has resulted in an increasing interest in this field. Ultra-thin TiO_x films were grown on Au(111) substrates in this work. Two well-ordered structures within monolayer coverage - honeycomb (HC) and pinwheel - were generated and investigated. Special attention has been paid to the uniform (2 x 2) Ti₂O₃ HC phase including its regular structure and imperfections such as domain boundaries (DBs) and point defects. Linear DBs with long-range repeating units have been observed; density functional theory (DFT) modelling has been used to simulate their atomic structures and calculate their formation energies. Rotational DBs/defects show up less frequently, however a six-fold symmetrical 'snowflake' DB loop stands out. Two types of point defects have been discovered and assigned to Ti vacancies and oxygen vacancies/hydroxyl groups. Their diffusion manners and pairing habits have been discussed within an experimental context. The results of growing NbO_x ultra-thin films on Au(111) are also presented in this thesis. An identical looking (2 x 2) HC structure to the Ti₂O₃ ultra-thin film has been formed; a stoichiometry of Nb2O3 is suggested. Another interesting reconstruction is a hollow triangle structure. Various sizes have been found, and sides of these equilateral triangles all show a double-line feature aligned along the { 1 ₁⁻ } directions of the Au(111) lattice. Chemical composition characterisations of NbO_x thin films are still required as is DFT modelling. Experimental techniques used in this thesis include scanning tunnelling microscopy (STM), low energy electron diffraction (LEED), and X-ray photoelectron spectroscopy (XPS). Ultra-thin oxide films were created by physical vapour deposition (PVD) in ultra-high vacuum (UHV) systems.

Le but de cette thèse est d'étudier l'effet de l’alignement et le contrôle de la morphologie de films minces de polythiophènes et de les corréler avec les propriétés optiques, de transport de charges et thermoélectriques. Puisque les polymères semiconducteurs sont intrinsèquement anisotropes, il est essentiel de les aligner afin de comprendre leur propriétés. Cette étude a été réalisée en employant deux techniques qui ont permises d’obtenir des films minces orientés. Le brossage à haute température et la cristallisation épitaxiale directionnelle (CED) ont conduit à des films de polythiophène hautement orientés avec des paramètres d'ordre allant jusqu'à 0.87 et des taux de crystallinité jusqu'à 65%. La technique de brossage nous a permis de contrôler avec précision les tailles des domaines cristallins dans des films de P3HT brossés. Par cette méthode, nous avons pu également déterminer les températures de fusion à l'équilibre de différents poly(3-alkyl-thiophène). Nous avons appris que la largeur de bande du couplage excitonique W dépend des dimensions des cristaux dans les films minces brossés. Cette étude à aussi montrer l’importance de la planarité des chaînes pontant les domaines cristallins à travers les zones amorphes sur les propriétés de transport de charges. Nous avons également mis en évidence la morphologie particulière du poly (3-butylthiophène) (P3BT) et le rôle des groupements butyles. La méthode de cristallisation epitaxialle a été utilisée pour orienter des films de poly(3-dioctylphenyl-thiophène) (PDOPT). Nous avons examiné l'effet de la masse moléculaire du PDOPT sur le degré de cristallinité et l'alignement. Ceci nous a permis de proposer un modèle structural montrant l’absence de pi-stacking dans ce polythiophène. Finalement, nous proposons une méthode en deux étapes d’élaboration de films minces conducteurs alignés. Le brossage des films puis le dopage des polymères semiconducteurs de type-P a permis d’obtenir des propriétés thermoélectriques anisotropes améliorées.Cette thèse démontre l'importance du contrôle de la morphologie et de l'alignement des polymères semiconducteurs et conducteurs pour comprendre leurs propriétés fortement anisotropes. / The aim of this thesis is to study the effect of alignment and morphological control on polythiophene thin films and to correlate this control with the optical, charge transport and thermoelectric properties. Since semiconducting polymers are inherently anisotropic by nature, studying these polymers in the aligned state was essential to understand their properties. This study could be achieved by employing two techniques that are successful in orienting polymers in thin films. High-temperature rubbing (HTR) along with directional epitaxial crystallization (DEC) produced highly oriented polythiophene thin films with order parameters reaching 0.87 and crystallinities up to 65%. HTR was a successful method to control crystal sizes in rubbed poly(3-hexyl-thiophene) P3HT films. By this method, the equilibrium melting temperatures of other poly(3-alkyl-thiophene) P3ATs were calculated. We learned that the free excitonic bandwidth depends on the crystal dimensions in the rubbed thin films. We also learned that the planarity of tie-chains linking consecutive crystalline domains plays a very important role in field-effect mobility. We also discuss the peculiar morphology of poly(3-butyl-thiophene) (P3BT) and the role of the butyl side groups. Then DEC method was proposed to orient poly(3-dioctylphenyl-thiophene) (PDOPT) thin films. We examined the effect of molecular weight of PDOPT on the level of crystallinity and alignment. Consequently, this relation provided fundamental information that helped us refine the crystal structure of PDOPT. Finally, a versatile method to produce highly aligned conducting polymers was proposed. HTR followed by P-type doping proved to be an excellent way to produce highly aligned conducting thin films with enhanced thermoelectric properties. This thesis brings value to the importance of morphology control and the alignment of semiconducting thin films to understand the various properties of these highly anisotropic systems.