Adhesion between solid bodies plays a prominent role in a wide variety of situations ranging from tribological applications to dust coagulation initiating the formation of planets. It can be due to various reasons like capillary, electrostatic, van der Waals, and hydrophobic forces. Among these, adhesion due to van der Waals force| which has its origin in permanent or instantaneous electric dipoles present in all atoms and molecules|is of special significance as it is present in all cases. Computational studies on adhesion due to van der Waals force commonly assume it as a surface force due to its short effective range, which is about a few tens of nanometers, in comparison to the length-scales commonly encountered. However, such restrictions are often violated in various important problems. For example, the characteristic dimensions of asperities| which are the smallest roughness elements interacting to cause friction and wear| are usually of nanometer length-scale. In addition, the assumptions inherent in development of surface force model are exact only when the deformations are small. In all such situations, the van der Waals force must be assumed as distributed over the volume. In this work, a computational model is developed by incorporating van der Waals force and short-range repulsion (steric repulsion or Pauli repulsion) as body forces distributed over the volume in a large deformation, static/transient, finite element framework. First the development of the general formulation is discussed, and then it is specialized for various considerations like handling symmetry and interaction between an elastic body and a rigid half-space, which offer significant computational advantages over the general formulation. The applicability of the model is illustrated by using a number of benchmark and practical problems. The comparison of the analysis results and well-established analytical models are provided, which validates our method. As a specific example, the smooth change of interaction force from a thin-rod model to a at-plate model on increasing the cross-sectional areas of two interacting elastic rods is demonstrated. The impact of elastic bodies in presence adhesion, and the associated energy loss is an important concern in studies regarding the origin of friction. Therefore, adhesive impact of elastic rods and spheres is studied using our formulation. Emphasis of the study is on finding the apparent energy loss during impact, which represents the part of energy lost to elastic stress waves remaining in the body after the impact, and hence not available for rebound motion. In case of impact of elastic rods on a rigid half-space, it is shown that the apparent energy loss is a unique function of the tensile strain energy developed in the rod due to van der Waals attraction. A one-dimensional model is developed for this case to determine the energy loss based on the specified problem parameters, which can be used to predict practically relevant phenomena like capture. In case of impact of elastic spheres, which is often correlated with asperity interactions, the energy loss is found to be significant only if adhesion-induced instabilities occur. The behavior shown by rods and spheres are probably at the two extremes with regards to energy loss during impact of elastic bodies in presence of adhesion. Practical use of the formulation is demonstrated by applying it to the study of amplitude variation and phase shifts in tapping-mode atomic force microscopy. Specifically, the advantage of operating the AFM cantilever just below its natural frequency as compared to operating it just above the natural frequency is demonstrated. Bistable behavior, which is the coexistence of two stable vibration modes under exactly same operating conditions, is shown to be severe when the driving frequency is higher than the natural frequency of AFM cantilever even in the absence of adhesion, which can result in spurious contrast-reversal artifacts during imaging. The hysteresis loop associated with the bistable behavior may lead to erroneous conclusions regarding presence of adhesion. Since this model overcomes the limitations of lumped parameter models and the computational models based on surface force approximation, the results can be used for much more realistic interpretation of experimental data. Computational framework developed in this study achieves the capability for analysis of adhesive contact problems directly from van der Waals interaction and steric repulsion. Such a model can be used for revisiting the fundamental problems in contact mechanics, as well as for providing better insights into experimental observations.

La microscopie à force atomique (AFM) permet de visualiser la topographie d’échantillons organiqueset inorganiques à l’échelle atomique. Les innovations les plus récentes offrent désormais la possibilitéd’accéder aux propriétés nano-mécaniques des échantillons (élasticité, adhésion…). Son panel defonctionnalités permet de pallier aux besoins des nanotechnologies, tant dans les domaines de laphysique, de la chimie que de la biologie.Cependant, les besoins nécessaires à la compréhension des processus biologiques imposent aumicroscope à force atomique des vitesses d’acquisitions rapides, inférieures à la seconde par image. Leséquipements classiques n’offrent pas cette possibilité. C’est pour s’affranchir de ce verrou technologique,pour l’étude dynamique, qu’un prototype de microscope à force atomique à haute-vitesse a étédéveloppé (HS-AFM) en partenariat avec l’équipe du Professeur T. Ando à l’Université de Kanazawa(Japon). Il permet d’atteindre des vitesses de balayage identiques aux vitesses vidéos : 25-50 images/s, enmilieu liquide. Le dispositif est en perpétuelle amélioration : nouvelle boucle d’asservissement, domainesde balayage augmentés. La haute résolution est, quant à elle, assurée par des leviers miniaturisés munisde sur-pointes en carbone. Parallèlement à l’innovation du microscope en lui-même, des modulescomplémentaires ont été développés : module pousse seringue et module chauffant.Le potentiel de ce prototype, développé dans le cadre d’un programme ANR PNANO 2008 HSnanobio-Imaging, a été montré via l’étude d’une petite protéine de choc thermique : la protéine sHspLo18. Cette protéine, issue de la bactérie lactique Oenococcus oeni, offrait la possibilité d’étudier deschangements de degrés d’oligomérisation en fonction du pH, ainsi que le rôle chaperon et lipochaperonen cas de stress environnemental d’autres complexes biologiques. L’utilisation des techniques demicroscopie couplée à des études biochimiques sur ce modèle protéique a permis d’appréhender l’effetdes surfaces sur l’adsorption et la dynamique des complexes biologiques. L’interaction protéine – surfacea pu être approchée et s’avère utile au développement des capteurs à protéines / The atomic force microscopy (AFM) gives access to the topography of organic and inorganic samplesat the atomic scale. The latest innovations offer the possiblity to understand the sample nano-mechanicalproperties (elasticity, adhesion...). Its feature set allows overcoming the demands of nanotechnology,both in the fields of physics, chemistry and biology.However, understanding biological processes require faster acquisitions for the atomic forcemicroscopy, less than a second per frame. As conventional equipment does not offer the possibility toovercome the constraint of time for dynamical studies, a prototype of high-speed atomic forcemicroscope (HS-AFM) was developed in partnership with Professor T. Ando group of Kanazawa University(Japan). It can reach scanning video speed: 25-50 frames/s in a liquid medium. The device is beingconstantly improved: new feedback control, larger scanning sizes. The resolution is provided byminiaturized cantilevers with carbon EBD-tips. In parallel to innovative modules on the microscope, addonshave been developed: syringe pump and heating modules.The potential of the prototype, developed within the framework of the program ANR PNANO 2008HS-nanobio-Imaging, has been shown through the study of a small heat shock protein: the protein sHspLo18. This protein, from the lactic acid bacterium Oenococcus oeni, offered the possibility of a variouschanges of oligomerization degrees according to the pH, and also the chaperone and lipochaperon activityof protein under the influence of an environmental stress. The use of these techniques of microscopiescoupled with biochemical studies on this proteic model allowed to dread the effect of surfaces on theadsorption and the dynamics of biological complexes. The interaction protein – surface coulb be toapprehend and proves to be useful for the development of protein sensors developed in the laboratory

Ternary lipid mixtures composed of cholesterol, saturated (frequently with sphingosine backbone), and unsaturated phospholipids show stable phase separation and are often used as model systems of lipid rafts. Yet, their ability to reproduce raft properties and function is still debated. We investigated the properties and functional aspects of three lipid raft model systems of varying degrees of biological relevance – PSM/POPC/Chol, DPPC/POPC/Chol, and DPPC/DOPC/Chol – using 2H solidstate nuclear magnetic resonance (NMR) spectroscopy, fluorescence microscopy, and atomic force microscopy. While some minor differences were observed, the general behavior and properties of all three model mixtures were similar to previously investigated influenza envelope lipid membranes, which closely mimic the lipid composition of biological membranes. For the investigation of the functional aspects, we employed the human N-Ras protein, which is posttranslationally modified by two lipid modifications that anchor the protein to the membrane. It was previously shown that N-Ras preferentially resides in liquid-disordered domains and exhibits a time-dependent accumulation in the domain boundaries of influenza envelope lipid membranes. For all three model mixtures, we observed the same membrane partitioning behavior for N-Ras. Therefore, we conclude that even relatively simple models of raft membranes are able to reproduce many of their specific properties and functions.

Aim of this student research project was to develop an Aluminium Oxide (Al2O3 ) ALD process from trimethylaluminum (TMA) and Ozone in comparison of two shower head designs. Then studying the detailed characteristics of Al2O3 ALD process using various measurement techniques such as Spectroscopic Ellipsometry (SE), x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM). The real-time ALD growth was studied by in-situ SE. In-situ SE is very promising technique that allows the time-continuous as well as time-discrete measurement of the actual growth over an ALD process time. The following ALD process parameters were varied and their inter-dependencies were studied in detail: exposure times of precursor and co-reactant as well as Argon purge times, the deposition temperature, total process pressure, flow dynamics of two different shower head designs. The effect of varying these ALD process parameters was studied by looking upon ALD cycle attributes. Various ALD cycle attributes are: TMA molecule adsorption (Mads ), Ligand removal (Lrem ), growth kinetics (KO3 ) and growth per cycle (GPC).:List of abbreviations and Symbols ........................XII Lists of Figures and Tables ...................................XVIII 1 Introduction .......................................................1 I Theoretical Part ..................................................3 2 Alumina in electronic industry ............................5 3 Atomic Layer Deposition ....................................7 3.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 3.2 Process definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 3.3 Benefits and limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 3.4 ALD growth mechanism of Aluminium oxide from TMA/O 3 . . . . . . . . 9 3.5 Growth kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 3.6 Comparison of TMA/O3 and TMA/H2O – A literature survey . . . . 14 4 Spectroscopic Ellipsometry .....................................................17 4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 4.2 Measuring Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 4.3 Fitting and models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 4.4 Advantages and limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 5 X-Ray Photoelectron Spectroscopy ..............................................25 5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 5.2 XPS mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 5.3 XPS analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 5.4 Advantages and limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 6 Atomic Force Microscopy .............................................................29 II Experimental Part ......................................................................31 7 Methodologies ............................................................................33 7 .1 Experimental setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 7 .2 ALD process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36 7 .3 Experiment design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36 7 .4 Spectroscopic Ellipsometry . . . . . . . . . . . . . . . . . . . . . . . . . . . 38 7 .4.1 Tool and software . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38 7 .4.2 Data acquisition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38 7 .4.3 Data evaluation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40 7 .4.4 Post processing of data . . . . . . . . . . . . . . . . . . . . . . . . . 41 7 .4.5 Sources of errors in SE . . . . . . . . . . . . . . . . . . . . . . . . . 43 8 Results and discussion ..........................................................47 8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48 8.2 Kinetic ALD characteristic curves . . . . . . . . . . . . . . . . . . . . . . . . 48 8.2.1 TMA exposure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49 8.2.2 Argon purging after TMA exposure . . . . . . . . . . . . . . . . . . . 50 8.2.3 Ozone exposure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51 8.2.4 Argon purging after ozone exposure . . . . . . . . . . . . . . . . . . 52 8.3 Impact of process parameters on characteristic ALD growth attributes and film properties . . . . . . . . . .. . . . . . . . . . . . . . . . 53 8.3.1 Total process pressure . . . . . . . . . . . . . . . . . . . . . . . . . . 53 8.3.2 Ozone flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54 8.3.3 Deposition temperature . . . . . . . . . . . . . . . . . . . . . . . . . 56 8.4 Reproducibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61 9 Conclusions and outlook .......................................................63 References ...............................................................................68 III Appendix .............................................................................77 A Reference temperatures and ozone flow.............................. 79 B Process parameters ..............................................................81

Interactions of cells with their environment regulate important cellular functions and are required for the organization of cells into tissues and complex organisms. These interactions involve different types of adhesion receptors. Interactions with extracellular matrix (ECM) proteins are mainly mediated by the integrin family of adhesion molecules. Situations in which integrin-ECM interactions are deregulated cause diseases and play a crucial role in cancer cell invasion. Thus, the mechanisms underlying integrin-binding and regulation are of high interest, particularly at the molecular level. How can cell-ECM interactions be studied? While there are several methods to analyze cell adhesion, few provide quantitative data on adhesion forces. One group, single-cell force spectroscopy (SCFS), quantifies adhesion at the single-cell level and can therefore differentiate the adhesive properties of individual cells. One implementation of SCFS is based on atomic force microscopy (AFM); this technique has been employed in the presented work. Advantageously AFM-SCFS combines high temporal and spatial cell manipulation, the ability to measure a large range of adhesion forces and sufficiently high-force resolution to allow the study of single-molecule binding events in the context of a living cell. Since individual adhesion receptors can be analyzed within their physiological environment, AFM-SCFS is a powerful tool to study the mechanisms underlying integrin-regulation. The presented work is split into six chapters. Chapter one gives background information about cell-ECM interactions. In chapter two, different adhesion assays are compared and contrasted. The theoretical Bell-Evans model which is used to interpret integrin-mediated cell adhesion is discussed in chapter three. Thereafter, the three projects that form the core of the thesis are detailed in chapters four through six. In the first project (chapter 4), α2β1-integrin mediated cell adhesion to collagen type I, the most abundant structural protein in vertebrates, was quantified using CHO cells. Firstly, α2β1-collagen interactions were investigated at the single-molecule level. Dynamic force spectroscopy permitted calculation of bond specific parameters, such as the bond dissociation rate koff (1.3 ± 1.3 sec-1) and the barrier width xu (2.3 ± 0.3 Å). Next, α2β1-integrin mediated cell adhesion to collagen type I was monitored over contact times between 0 and 600 sec. Thereby the kinetics of α2β1-integrin mediated interactions was explored and insights into the underlying binding mechanisms were gained. In the second project (chapter five), effects of cryptic integrin binding sites within collagen type I exerted on pre-osteoblasts were investigated. Collagen type I matrices were thermally denatured which lead to exposure of cryptic RGD (Arg-Gly-Asp)-motifs. As a consequence pre-osteoblasts enhanced their adhesion to denatured collagen. Compared to native collagen type I, adhesion to denatured collagen was mediated by a different set of integrins, including αv- and α5β1-integrins. Cells grown on denatured collagen showed enhanced spreading and motility, which correlated with increased focal adhesion kinase phosphorylation levels. Moreover, osteogenic differentiation kinetics and differentiation potential were increased on denatured collagen. The findings of this project open new perspectives for optimization of tissue engineering substrates. In the third part (chapter six), the effect of the fusion protein BCR/ABL, a hallmark of chronic myeloid leukemia, on adhesion of myeloid progenitor cells was studied. Adhesion between BCR/ABL transformed progenitor cells to bone marrow derived stromal cells and to different ECM proteins was quantitatively compared to that of control cells. The tyrosine kinase activity of BCR/ABL enhanced cell adhesion, which was blocked by imatinib mesylate, a drug interfering with BCR/ABL activity. BCR/ABL-enhanced adhesion correlated with increased β1-integrin cell surface concentrations. Since adhesion of leukemic cells to the bone marrow compartment is critical for the development of drug resistance, the reported results may provide a basis for optimized target therapies. In the three described projects AFM-based SCFS was applied to investigate early steps of integrin-mediated adhesion at the molecular level. Taken together, the results demonstrate that AFM-SCFS is a versatile tool that permits monitoring of cell adhesion from single-molecule interactions to the formation of more complex adhesion sites at the force level. / Interaktionen zwischen Zellen und ihrer Umgebung sind maßgeblich an der Regulierung zellulärer Funktionen beteiligt und daher notwendig für die Organisation von Zellen in Geweben und komplexen Organismen. Zellinteraktionen mit der extrazellulären Matrix (EZM) werden hauptsächlich durch Integrine vermittelt. Situationen, in denen Integrin- EZM Interaktionen verändert sind, können Krankheiten verursachen und spielen zudem eine wichtige Rolle bei der Invasion von Krebszellen. Daher besteht ein großes Interesse darin, die molekularen Mechanismen, die Integrin-EZM Interaktionen regulieren, besser zu verstehen. Wie können Zell-EZM Interaktionen untersucht werden? Obwohl es mehrere Methoden gibt, mit denen Zelladhäsion untersucht werden kann, sind die wenigsten dazu geeignet, Zelladhäsionskräfte zu quantifizieren. Einzelzellspektroskopie erfasst die Adhäsionskräfte einzelner Zellen quantitativ und ermöglicht dadurch eine differenzierte Betrachtung der Adhäsion individueller Zellen. Eine Variante der Einzelzellspektroskopie basiert auf der Rasterkraftmikroskopie (AFM); diese Technik wurde in der vorliegenden Arbeit verwendet. Ein Vorteil von AFM- Einzelzellspektroskopie besteht darin, dass Zellen mit hoher zeitlicher und räumlicher Präzision manipuliert werden können. Zelladhäsionskräfte können zudem über einen großen Kraftbereich hinweg untersucht werden. Dabei ermöglicht es die hohe Kraftauflösung, einzelne Integrin-Ligandenbindungen in lebenden Zellen zu untersuchen. Die vorliegende Arbeit gliedert sich in sechs Kapitel. Kapitel eins gibt Hintergrundinformationen über Zell-EZM Wechselwirkungen. In Kapitel zwei werden verschiedene Adhäsionsassays einander gegenüber gestellt. Das theoretische Bell-Evans Modell, mit dessen Hilfe die gewonnenen Daten interpretiert wurden, wird in Kapitel drei diskutiert. Im Anschluss werden drei Projekte, welche das Herzstück dieser Doktorarbeit bilden, in Kapiteln vier bis sechs näher ausgeführt. Im ersten Projekt (Kapitel vier) wurde die Adhäsion von α2β1-Integrin exprimierenden CHO Zellen zu Kollagen I, dem häufigsten strukturellen Protein in Wirbeltieren, quantitativ untersucht. Zunächst wurden α2β1-Kollagen-Interaktionen auf Einzelmolekülebene analysiert. Mithilfe der dynamischen Kraftspektroskopie wurden für diese Bindung Dissoziationsrate koff (1.3 ± 1.3 sec-1) und Potentialbarrierenbreite xu (2.3 ± 0.3 Å) bestimmt. Daraufhin wurde die α2β1-vermittelte Adhäsion über einen Zeitraum von zehn Minuten untersucht. Dadurch konnten Einblicke in die Kinetik von α2β1-integrin vermittelter Zelladhäsion sowie in die zugrunde liegenden Regulationsmechanismen gewonnen werden. Im zweiten Projekt (Kapitel fünf) wurde die Rolle von kryptischen Integrin-Bindungsstellen in Kollagen I untersucht. Die zuvor verwendeten Kollagenoberflächen wurden thermisch denaturiert, wodurch versteckte RGD (Arg-Gly-Asp)-Sequenzen freigelegt wurden. Die partielle Denaturierung hatte- verglichen mit nativem Kollagen I- eine erhöhte Adhäsion von Präosteoblasten (MC3T3-E1) zur Folge, was auf das Binden zusätzlicher Integrine zurückgeführt wurde. Im Unterschied zu nativem Kollagen wurde die Zelladhäsion zu denaturiertem Kollagen I u.a. durch αv- and α5β1-Integrine vermittelt. Präosteoblasten zeigten verstärktes Zellspreiten sowie höhere Motilität auf denaturiertem Kollagen I; zudem wurde ein erhöhtes Differenzierungpotential der Präosteoblasten festgestellt. Die in diesem Projekt erhaltenen Einblicke bilden eine hilfreiche Basis für die Entwicklung optimierter Oberflächen für diverse Zell- und Gewebekulturanwendungen. Im dritten Projekt (Kapitel sechs) wurde der Einfluss des Fusionproteins BCR/ABL, charakteristisch für chronische myeloische Leukämie, auf die Adhäsion von myeloischen Vorläuferzellen untersucht. Dazu wurde die Adhäsion von BCR/ABL transformierten Vorläuferzellen (32D Zellen) bzw. Kontrollzellen zu Stromazellen (M2-10B4) sowie verschiedenen EZM Proteinen untersucht. BCR/ABL erhöhte die Zelladhäsion der myeloischen Vorläuferzellen signifikant. Dieser Effekt wurde durch die Zugabe von Imatinib, welches die Tyrosinkinaseaktivität von BCR/ABL inhibiert, aufgehoben. Die BCR/ABL-verstärkte Zelladhäsion korrelierte mit erhöhten β1-Integrin-konzentrationen. Da die Adhäsion von Leukämiezellen im Knockenmark bekanntermaßen kritisch für die Entwicklung von Resistenzen gegenüber verschiedenen Wirkstoffen ist, könnten die Ergebnisse dieser Studie eine Grundlage für die Entwicklung optimierter Target-Therapien sein. In den drei beschriebenen Projekten wurde AFM Einzelzellspektroskopie verwendet, um Integrin- vermittelte Adhäsion auf molekularer Ebene zu untersuchen. Die Ergebnisse zeigen, dass AFM-Einzelzellspektroskopie ein vielseitiges Werkzeug darstellt, das überaus geeignet dazu ist, Zelladhäsion- ausgehend von Einzelmolekülinteraktionen bis hin zur Entstehung komplexerer Adhäsionsstellen- auf der Kraftebene zu verfolgen.

Das chemisch-mechanische Planarisieren (CMP) in der Halbleiterindustrie ist ein Prozess mit sehr vielen Einflussgrößen, wobei das Polierergebnis unter anderem von den Eigenschaften der Wechselwirkungskomponenten Wafer, Poliersuspension und Polierpad abhängig ist. Bei der Entwicklung neuer Schaltkreisentwürfe werden die strukturellen Abhängigkeiten der Topografie nach dem CMP häufig im Verlauf von zeit- und kostenintensiven Lernzyklen aufgedeckt und angepasst. Um Dauer und Kosten für die Entwicklung neuer Schaltkreise zu reduzieren, sollte im Rahmen eines BMBF-Projektes ein umfassendes Gesamtmodell, welches den Polierprozess ausführlich beschreibt, entwickelt werden. Für die Umsetzung dieses Vorhabens ist ein umfassendes qualitatives und quantitatives Verständnis der mechanisch-hydrodynamischen und physikalisch-chemischen Mechanismen zu erarbeiten, welche den Materialabtrag und die Planarisierung beim CMP bestimmen. Ziel der vorliegenden Arbeit war es zum einen, mittels direkter Kraftmessung am AFM die Wechselwirkungskräfte zwischen den Festkörperoberflächen von Schleifpartikel und Wafer sowie zwischen den Schleifpartikeln untereinander in CMP-relevanten Flüssigkeiten und ihre Bedeutung für das CMP zu untersuchen. Um die Wechselwirkungskräfte am AFM bestimmen zu können, war zuvor die Entwicklung einer geeigneten Versuchsanordnung nötig. Zur Absicherung der Ergebnisse aus den Kraftmessungen wurde eine Methode erarbeitet, um die zwischenpartikulären Wechselwirkungen mittels rheologischer Untersuchungen indirekt bestimmen zu können. Des Weiteren fanden rheologische Messungen zur Untersuchung der Fließeigenschaften der Poliersuspensionen statt, wobei außerdem der Einfluss anwendungsrelevanter hydrodynamischer Kräfte auf die Stabilität der Poliersuspension zu überprüfen war. Als Poliersuspensionen kamen kommerziell verfügbare Slurries sowie eine Modellslurry zum Einsatz. Neben Systemen mit dispergierten Silica-Partikeln wurde auch eine Slurry mit Ceria-Partikeln als disperse Phase betrachtet. Die kontinuierliche Phase einer Poliersuspension ist ein Mehrkomponentensystem und enthält unterschiedlichste Additive. Untersucht wurde der Einfluss von pH-Wert und Elektrolytkonzentration auf die Wechselwirkungskräfte, das Fließverhalten sowie den Materialabtrag.

A commercial non-contact atomic force microscope was improved to achieve utmost resolution on a routine basis. This system was used to study the (110) surface of rutile titanium dioxide. The focus was on understanding contrast formation in terms of tip-sample interaction mechanisms. Moreover, chromium and antimony-doped titanium dioxide was investigated. The implications of transition-metal doping on the surface structure of this highly interesting photocatalyst was studied at the atomic scale.

Endocytosis is one of the most fundamental mechanisms by which the cell communicates with its surrounding. Specific signals are transduced through the cell membrane by a complex interplay between proteins and lipids. Clathrin depended endocytosis is one of important signalling pathways which leads to budding of the plasmalemma and a formation of endosomes. The FCHo2 is an essential protein at the initial stage of the this process. In is a membrane binding protein containing BAR (BIN, Amphiphysin, Rvs) domain which is responsible for a membrane binding. Although numerous valuable work on BAR proteins was published recently, the mechanistic description of a BAR domain functionality is missing. In present work we applied in vitro systems in order to gain knowledge about molecular basis of the activity of the FCHo2 BAR domain. In our studies we used supported lipid bilayers (SLBs) and lipid monolayers as s model membrane system. The experiments were carried out with a minimal number of components including the purified FCHo2 BAR domain. Using SLBs we showed that the BAR domain can bind to entirely flat bilayers. We also demonstrated that these interactions depend on the negatively charged lipid species incorporated in the membrane. We designed an assay which allows to quantify the membrane tubulation. We found out that the interaction of the FCHo2 BAR domain with the lipid membrane is concentration dependent. We showed that an area of the bilayer deformed by the protein depends on the amount of the used BAR domain. In order to study the relation between the mobility of lipids and the activity of FCHo2 BAR domain we designed a small-volume monolayer trough. The design of this micro-chamber allows for the implementation of the light microscopy. We demonstrated that the measured lipid diffusion in the monolayer by our new approach is in agreement with literature data. We carried out fluorescence correlation spectroscopy (FCS) experiments at different density of lipids at the water-air interface.We showed that the FCHo2 BAR domain binding affinity is proportional to the mean molecular area (MMA). We additionally demonstrated that the increased protein binding is correlated with the higher lipid mobility in the monolayer. Additionally, by curing out high-speed atomic force microscopy (hsAFM) we acquired the structural information about FCHo2 BAR domains orientation at the membrane with a high spatio-temporal resolution. Obtained data indicate the BAR domains interact witheach other by many different contact sites what results in a variety of protein orientations in a protein assemble.

Ce manuscrit est consacré à l’analyse théorique et expérimentale d’oxydes Ln2Ti2O7 (Ln = La, Nd, Sm, Gd) et BiFeO3.Les propriétés physiques de La2Ti2O7 et Nd2Ti2O7 ont été investiguées au moyen de calculs ab initio, confirmant ainsi leur ferroélectricité. D’autres oxydes de la famille Ln2Ti2O7, Sm2Ti2O7 et Gd2Ti2O7, ont ensuite été étudiés selon les mêmes méthodes théoriques. Nos calculs ont révélé une meilleure amplitude de polarisation pour ces composés par rapport au La2Ti2O7 et au Nd2Ti2O7. La deuxième partie de ce travail est consacrée aux propriétés structurales, électroniques et ferroélectriques du BiFeO3. L’évolution de ses propriétés lorsqu’il est soumis à une contrainte épitaxiale ont été investiguées au moyen de calculs ab-initio et de mesures en microscopie à champ proche réalisées sur des couches minces déposées sur un substrat de SrTiO3(001). Nos résultats mettent en évidence une modification de la structure interne du matériau sous effet de contrainte, qui se traduit par une réorientation progressive de la polarisation spontanée suivant la direction [001]. Notre étude s’est ensuite tournée vers l’élaboration et l’analyse des propriétés structurales et ferroélectriques de superréseaux (SrTiO3)n(BiFeO3)m. Nos calculs ont mis en évidence que la contrainte épitaxiale imposée au superréseau offrait un contrôle accru des propriétés du BiFeO3 par rapport à son comportement lorsqu’il est déposé seul en couches minces. Les analyses en microscopie à champ proche ont montré une réduction de la tension coercitive de tels films par rapport à celle mesurée sur des bicouches SrTiO3/BiFeO3 ou sur une couche mince de BiFeO3. / In this work, first-principles calculations and experimental measurements have been done in order to investiguate the structural, electroniq and ferroelectric properties of Ln2Ti2O7 (Ln = La, Nd, Sm, Gd) and BiFeO3 oxydes. Calculations on La2Ti2O7 and Nd2Ti2O7 confirmed their ferroelectricity. Other oxydes belonging to the Ln2Ti2O7 family have also been investigated. The results showed an enhancement of the spontaneous polarization within these compounds compared to that of La2Ti2O7 and Nd2Ti2O7. The second part of this work is related to the structural and ferroelectric properties of bismuth ferrite BiFeO3. The evolution of its properties when undergoing an epitaxial strain have been investigated by ab initio calculations and piezoresponse force microscopy measurements on thin films deposited on a (001)-SrTiO3 substrate. Our results showed a modification of the inner structure of BiFeO3 under stain, leading to a continuous reorientation of the spontaneous polarization vector towards [001]. The third part of our study consists in the computational design and synthesis of (SrTiO3)n(BiFeO3)m superlattices. Our calculations showed that epitaxial strain imposed to the superlattice brings a further control of physical properties of BiFeO3 as compared with its behaviour when deposited alone in a thin film. PFM analysis showed a decrease of the coercive field for STO/LNO/(STO)n(BFO)m superlattices as compared with those measured on STO/BFO bi-layers and on BiFeO3 thin films.

Un microscope à force atomique (AFM) est utilisé pour caractériser des matériaux isolant ou semi-conducteur avec une résolution pouvant atteindre l'échelle atomique. Ce microscope est constitué d'un capteur de force couplé à une électronique de contrôle pour pouvoir correctement caractériser ces matériaux. Parmi les différents modes (statique et dynamique), nous nous focalisons essentiellement sur le mode dynamique et plus particulièrement sur le fonctionnement sans contact à modulation de fréquence (FM-AFM). Dans ce mode, le capteur de force est maintenu comme un oscillateur harmonique par le système d'asservissement. Le projet ANR Pnano2008 intitulé : ”Cantilevers en carbure de silicium à piézorésistivité métallique pour AFM dynamique à très haute fréquence" a pour objectif d'augmenter significativement les performances d'un FM-AFM en développant un nouveau capteur de force très haute fréquence. Le but est d'augmenter la sensibilité du capteur et de diminuer le temps nécessaire à l'obtention d'une image de la surface du matériau. Le système de contrôle associé doit être capable de détecter des variations de fréquence de 100mHz pour une fréquence de résonance de 50MHz. Etant donné que les systèmes présents dans l'état de l'art ne permettent pas d'atteindre ces performances, l'objectif de cette thèse fut de développer un nouveau système de contrôle. Celui-ci est entièrement numérique et il est implémenté sur une carte de prototypage basée sur un FPGA. Dans ce mémoire, nous présentons le fonctionnement global du système ainsi que ses caractéristiques principales. Elles portent sur la détection de l'écart de fréquence de résonance du capteur de force. / An atomic force microscope (AFM) is used to characterize insulating materials or semiconductors with a resolution up to the atomic length scale. The microscope includes a force sensor linked to a control electronic in order to properly characterize these materials. Among the various modes (static and dynamic), we focus mainly on the dynamic mode and especially on the frequency modulation mode (FM-AFM). In this mode, the force sensor is maintained as a harmonic oscillator by the servo system. The research project ANR Pnano2008 entitled: "metal piezoresistivity silicon carbide cantilever for very high frequency dynamic AFM" aims to significantly increase the performance of a FM-AFM by developing new very high frequency force sensors. The goal is to increase the sensitivity of the sensor and to decrease the time necessary to obtain topography images of the material. The control system of this new sensor must be able to detect frequency variations as small as 100mHz for cantilevers with resonance frequencies up to 50MHz. Since the state-of-the-art systems doe not present these performances, the objective of this thesis was to develop a new control system. It is fully digital and it is implemented on a FPGA based prototyping board. In this report, we present the system overall functioning and its main features which are related to the cantilever resonant frequency detection. This detection is managed by a phase locked loop (PLL) which is the key element of the system.