Energijos kaupiklių kūrimas pastaraisiais metais tapo svarbia mokslo aktualija. Elektrocheminiai kondensatoriai pasižymi didesne galia, ilgesniu savaiminio išsikrovimo laiku ir didesniu darbo ciklų skaičiumi negu tradicinės elektrocheminės baterijos. Didžiausia savitąja talpa pasižymi RuO2, tačiau jo praktinį taikymą riboja didelė kaina, todėl ieškoma pigesnių pakaitalų. Pastaraisiais metais aktyviai tiriamas kobalto oksidas. Svarbu yra surasti ekonomiškai efektyvius ir paprastus metodus, leidžiančius padidinti kobalto oksidų pseudotalpas. Darbe nustatytos elektrocheminio Co nusodinimo sąlygos, kurioms esant yra formuojama pluoštinė nanostruktūra, pasižyminti dideliu paviršiaus plotu. Anodinės poliarizacijos būdu buvo suformuoti kobalto hidro/oksido sluoksniai ir ištirta jų pseudotalpa ant skirtingų substratų: nanostruktūrinės, magnetroninės-plazminės dangos ir metalurginio Co. Pseudotalpinė kobalto hidro/oksidų elgsena buvo ištirta ciklinės voltamperometrijos metodu kartu su elektrocheminėmis kvarco kristalo svarstyklėmis (EKKM). Oksidiniai sluoksniai parodė grįžtamą redukcijos-reoksidacijos ir atitinkamą pseudotalpinę elgseną. Per kelis tūkstančius anodinių ciklų buvo parodyta, kad oksidinis sluoksnis išliko stabilus. Nustatyta, kad hidro/oksidų, suformuotų ant nanostruktūrinės Co dangos, talpa maždaug 5 kartus didesnė nei suformuotų ant metalurginio Co. Šiame darbe pasiūlytas naujas kobalto oksido formavimo būdas: sulfidinės Co(OH)2–CoS kompozicijos formavimas ir... [toliau žr. visą tekstą] / Design of high efficiency energy accumulators has recently become an important issue of science and technology. Electrochemical capacitors are distinguished for a greater power, a longer self-discharge time and a greater number of work cycles as compared to those of traditional electrochemical batteries. Effective supercapacitors are mainly produced of RuO2, which is distinguished from other metals for its nearly highest specific capacity, however its practical application is limited by its high price, therefore efforts are under way to find cheaper substitutes. Recently cobalt oxide has been intensively studied. It is important to find economically effective and simple methods which will make it possible to increase the pseudocapacities of cobalt oxides. The conditions of electrochemical cobalt deposition, under which the fiber Co nanostructure possessing a great surface area is formed, have been determined in the work. Cobalt hydro/oxide layers were formed by the anodic polarization method and their pseudocapacity was studied on various substrates: nanostructured, magnetron-sputtered coating and metallurgical cobalt. The pseudocapacitor behaviour of cobalt hydro/oxides was studied by using the cyclic voltammetry method along with electrochemical quartz crystal mocrobalance (EKKM). Oxide layers showed oxidation-reduction and corresponding pseudo-capacitor behaviour.It has been shown that the oxide layer is stable and it withstands a few thousand polarization cycles. It has... [to full text]

Design of high efficiency energy accumulators has recently become an important issue of science and technology. Electrochemical capacitors are distinguished for a greater power, a longer self-discharge time and a greater number of work cycles as compared to those of traditional electrochemical batteries. Effective supercapacitors are mainly produced of RuO2, which is distinguished from other metals for its nearly highest specific capacity, however its practical application is limited by its high price, therefore efforts are under way to find cheaper substitutes. Recently cobalt oxide has been intensively studied. It is important to find economically effective and simple methods which will make it possible to increase the pseudocapacities of cobalt oxides. The conditions of electrochemical cobalt deposition, under which the fiber Co nanostructure possessing a great surface area is formed, have been determined in the work. Cobalt hydro/oxide layers were formed by the anodic polarization method and their pseudocapacity was studied on various substrates: nanostructured, magnetron-sputtered coating and metallurgical cobalt. The pseudocapacitor behaviour of cobalt hydro/oxides was studied by using the cyclic voltammetry method along with electrochemical quartz crystal mocrobalance (EKKM). Oxide layers showed oxidation-reduction and corresponding pseudo-capacitor behaviour.It has been shown that the oxide layer is stable and it withstands a few thousand polarization cycles. It has... [to full text] / Energijos kaupiklių kūrimas pastaraisiais metais tapo svarbia mokslo aktualija. Elektrocheminiai kondensatoriai pasižymi didesne galia, ilgesniu savaiminio išsikrovimo laiku ir didesniu darbo ciklų skaičiumi negu tradicinės elektrocheminės baterijos. Didžiausia savitąja talpa pasižymi RuO2, tačiau jo praktinį taikymą riboja didelė kaina, todėl ieškoma pigesnių pakaitalų. Pastaraisiais metais aktyviai tiriamas kobalto oksidas. Svarbu yra surasti ekonomiškai efektyvius ir paprastus metodus, leidžiančius padidinti kobalto oksidų pseudotalpas. Darbe nustatytos elektrocheminio Co nusodinimo sąlygos, kurioms esant yra formuojama pluoštinė nanostruktūra, pasižyminti dideliu paviršiaus plotu. Anodinės poliarizacijos būdu buvo suformuoti kobalto hidro/oksido sluoksniai ir ištirta jų pseudotalpa ant skirtingų substratų: nanostruktūrinės, magnetroninės-plazminės dangos ir metalurginio Co. Pseudotalpinė kobalto hidro/oksidų elgsena buvo ištirta ciklinės voltamperometrijos metodu kartu su elektrocheminėmis kvarco kristalo svarstyklėmis (EKKM). Oksidiniai sluoksniai parodė grįžtamą redukcijos-reoksidacijos ir atitinkamą pseudotalpinę elgseną. Per kelis tūkstančius anodinių ciklų buvo parodyta, kad oksidinis sluoksnis išliko stabilus. Nustatyta, kad hidro/oksidų, suformuotų ant nanostruktūrinės Co dangos, talpa maždaug 5 kartus didesnė nei suformuotų ant metalurginio Co. Šiame darbe pasiūlytas naujas kobalto oksido formavimo būdas: sulfidinės Co(OH)2–CoS kompozicijos formavimas ir... [toliau žr. visą tekstą]

La diminution du coût des catalyseurs est l'une des conditions nécessaires pour rendre la technologie PEMFC économiquement viable au grand public. Ces catalyseurs, habituellement composés de nanoparticules de platine, sont limités par leur coût, leur performance et leur durabilité. La nanostructuration est une des solutions envisageables pour ces catalyseurs car elle permet d'augmenter considérablement la surface spécifique, de diminuer le chargement en platine et d'augmenter les performances pour la réaction de réduction de l'oxygène, la plus limitante dans la technologie PEMFC.Les travaux présentés dans ce mémoire, ont été réalisés autour de deux types de particules nanostructurées (particules coeur-coquille et particules creuses) à base de platine ou d'alliage de platine. Ces particules ont été étudiées, caractérisées en électrochimie à 3 électrodes (électrode tournante disque-anneau et montage demi-pile) puis intégrées dans des systèmes pile à combustible. Nous avons observé les améliorations de performances offertes par ce type de particules électro-catalytiques vis-à-vis de la réaction de réduction de l'oxygène. Puis nous avons commencé à étudier et à optimiser leur intégration dans les piles à combustible en conditions réelles de fonctionnement. / The decrease in cost of catalysts is one of the conditions necessary to make economically viable PEMFC technology to the general public. These catalysts, usually composed of platinum nanoparticles, are limited by cost, performance and durability. Nanostructuring is one of the possible solutions for these catalysts because it greatly increases the surface area, reducing the platinum loading and increase performance for the reaction of oxygen reduction, the most limiting in PEMFC technology.The works presented in this thesis were performed on two types of nanostructured particles (core-shell particles, hollow particles) based on platinum or platinum alloy. These particles have been studied, characterize in electrochemistry to 3 electrodes (rotating ring-disk electrode and half-cell assembly) and then integrated in fuel cell systems. We observed performance improvements offered by this type of electro-catalytic particles towards the reduction reaction of oxygen and then we started studying and optimize their integration into fuel cells and actual conditions of operation.

The current high demand for sustainable and renewable energy sources to solve world energy crisis has enormously increased interest in looking at alternative sources of energy. All the machines used in manufacturing process, electricity generation, residential applications, transportation etc., rejects energy in the form of heat into environment. Thermoelectric materials can convert thermal-to-electrical and electrical-to-thermal energy and can be utilized in waste-heat harvesting, more efficient cooling to reduce energy usage and CO2 emissions. Significant research efforts have been devoted over the past decade to thermoelectric materials, with particular emphasis being placed on combining materials selection with nanostructuring. The overarching goal was to reduce thermal conductivity through selective phonon scattering and thus boost the thermoelectric figure-of-merit (ZT). SiGe alloys, as well as superlattices and nanocomposites made from them, showed significant improvements upon nanostructuring and ZT exceeding one at high temperatures. Other group IV alloys were not studied in the context of thermoelectrics. However, SiSn alloys are widely studied for their optoelectronic properties because they were predicted to become direct-gap materials when Sn composition increased beyond about 50%. To address this gap, we study the thermoelectric properties of SiSn alloys. Furthermore, we develop an iterative full-band solver for the electron Boltzmann transport equation and use it to compute the electron and hole mobility and Seebeck coeffcient in SiSn alloys. The electronic structure of SiSn alloys was computed in the virtual crystal approximation from non-local empirical pseudopotentials, while the application of strain allowed us to extract the electron-phonon coupling deformation potentials for each alloy composition. We benchmark our code against available mobility data for Si and SiGe alloys and find that it accurately reproduces the measured values. Full phonon dispersion was computed from the adiabatic bond charge model, which was shown to accurately reproduce measured dispersion, and used in our phonon BTE solver to compute lattice thermal conductivities. Scattering rates include anharmonic phonon-phonon, impurity, isotope, alloy, and boundary mechanisms. The lowest thermal conductivity was obtained in SiSn alloys, which have been experimentally demonstrated with up to 18% Sn composition. This carries through when combined with calculations of electronic power factor, where mobilities and Seebeck coeffcients of SiSn alloys are comparable to those of SiGe. Furthermore, ZT is optimized through doping for every composition. The ZT improves dramatically at higher temperatures, reaching ZT of 1.9, 2.36 is obtained for Sn composition of 10% and 50% in a n-doped bulk SiSn alloys at a temperature of 1480 K. However, such high Sn composition of 50% is unlikely to be synthesized due to low solid solubility of Sn in Si. Lastly, we study the impact of nanostructuring in thin films on the ZT. We also establish the limits on how much the ZT can be improved through nanostructuring by studying thin films of SiSn alloys across temperature from room temperature up to 1500 K. We conclude that in bulk SiSn alloys, even at modest Sn concentration of 10%, ZT can reach 1.9, while in 20 nm thin films of n-type SiSn alloys, it can reach the long-sought target of ZT>3 and ZT of 2.16 is obtained in p-type nanostructured SiSn alloys.

Cette étude porte sur l’élaboration de polymères greffés à base de poly(éthylène alcool vinylique) (EVOH) et de la polycaprolactone (PCL). La réaction de greffage a lieu par la réaction d’alcoolyse entre les groupements ester de la polycaprolactone et les groupements alcools le long des chaînes d’EVOH. L’étude catalytique et cinétique par des études GC/MS très détaillées, facilitées par l’utilisation de réactions modèles avec le 1-dodécyl benzoate et le 2-dodécanol, montre la possibilité de la synthèse par extrusion réactive. L’activité catalytique de 1.5.7-triazabicyclo[4.4.0]dec-5-ene pour la réaction d’alcoolyse sans solvant et pas extrusion réactive a été confirmé. Les conditions de l’extrusion permettant un taux de greffage optimal ont été déterminées et l’effet déterminant de la température a été confirmé. Le taux de greffage peut être obtenu par des analyses 1H-RMN. Ces résultats combinés à la microscopie électronique à balayage et en transmission ont permis de déterminer les caractéristiques optimales des polymères employés afin de former des mélanges nanostructurés. Les mêmes conditions de synthèse appliqués à d’autres matériaux comme le polyméthacrylate de méthyle, acide polylactique et poly(3-hydroxybutyrate-co-3-hydroxyvalérate) ont permis l’élaboration des copolymères greffés pour des applications biomédicales / This study focuses on the development of graft polymers based on poly (ethylene vinyl alcohol) (EVOH) and polycaprolactone (PCL). The grafting reaction takes place by the alcoholysis reaction between ester groups of the polycaprolactone and alcohol groups along the chains of EVOH. The catalytic and kinetic studies by GC / MS highly detailed, facilitated by the use of model reactions with 1-dodecyl benzoate and 2-dodecanol, shows the possibility of synthesis by reactive extrusion. The catalytic activity of triazabicyclo-1.5.7 [4.4.0] dec-5-ene for the alcoholysis reaction without solvent and by reactive extrusion has been confirmed. The extrusion conditions for optimum rate of grafting were determined and the effect of temperature has been confirmed. The rate of grafting can be obtained by 1H-NMR analysis. These results combined with scanning electron microscopy and transmission, have determined the optimum characteristics of polymers to form nanostructured blends. The same synthesis conditions applied to other materials such as polymethylmethacrylate, polylactic acid and poly (3-hydroxybutyrate-co-3-hydroxyvalerate) allowed the preparation of graft copolymers for biomedical applications

La fabrication de surfaces polymères complexes avec des chimies et des topographies contrôlées à l’échelle micro et nanométrique est en pleine expansion en raison de la large gamme d'applications. Une nouvelle méthode prometteuse consiste à utiliser la photopolymérisation radicalaire contrôlée par les nitroxydes (NMP2) qui exploite une alcoxyamine photosensible (AA).Pour démontrer le potentiel de fabrication de surfaces de polymères complexes, un film de polymère a d'abord été formé en irradiant avec une formulation contenant un mélange de monomère acrylique et l’alcoxyamine. Ensuite, le dépôt d'un second monomère acrylique sur ce film durci peut redémarrer une nouvelle réaction de photopolymérisation du fait de la présence d'alcoxyamines à la surface. Les radicaux peuvent être réactivés par exposition aux lampes UV et permettent de commencer un nouveau procédé de polymérisation. Une autre alternative est d'utiliser l’écriture directe par laser pour produire des structures en 2D ou 2.5D de polymère, en déplaçant le faisceau laser sur la surface de l'échantillon.Un soin particulier a été axé sur l'impact de paramètres photoniques et chimiques sur le processus de repolymérisation. Les mécanismes moléculaires qui régissent la repolymérisation pourraient être déduits de cette étude.Certaines applications montrent le potentiel de l'alcoxyamine pour générer des surfaces hydrophiles / hydrophobes ou fluorescentes pour des applications avancées. / The fabrication of complex polymer surfaces with controled chemistry and topography at the micro and nanoscale has drawn a huge attention during the last years due to the wide range of applications. A promising new method consists in using the nitroxide mediated photopolymerization (NMP2). this method exploits a photosensitive alkoxyamine (AA) that creates latent reactive radical species.To demonstrate the potential for fabrication of complex polymer surfaces, a polymer film was first formed by irradiating with a formulation containing a mixture of acrylic monomer and alkoxyamine. Then, depositing a second acrylic monomer over this cured film can reboot a new photopolymerization reaction due to the presence of alkoxyamines at the surface. The radicals can be reactivated by exposure to UV and start a new polymerization process. Another alternative is to use UV-laser direct writing to produce 2D or 2.5D polymer structure by displacing the laser beam at the surface of the sample.A special care was focused on investigating the impact of photonic and chemical parameters on the extend of the repolymerization process. The molecular mechanisms governing the repolymerization could be deduced from this study.Some applications are provided showing the potential of the alkoxyamine for generating hydrophilic/hydrophobic or fluorescent surfaces for advanced applications.

No description available.

Dans l’optique d’aller toujours vers le plus petit, un réacteur plasma micro-ondes en cavité résonnante fonctionnant à la pression atmosphérique a été développé à l’Institut Jean-Lamour (IJL, UMR 7198) dans l’équipe ESPRITS (Expériences et Simulations des Plasmas Réactifs - Interaction plasma-surface et Traitement des Surfaces).Ce réacteur plasma présente la particularité de pouvoir fournir une post-décharge de petite dimension (de l’ordre du millimètre). Un mélange Ar-O2 est utilisé comme gaz composant le plasma. L’aspect filamentaire de ce type de plasma est une des caractéristiques majeures du dispositif. De plus, la post-décharge se trouve notamment composée d’oxygène atomique, espèce active très utilisée par exemple en PECVD ou pour la fonctionnalisation de surface.Notre travail a consisté à mettre au point ce réacteur plasma et à caractériser la post-décharge résultante. Après avoir maîtrisé les principaux paramètres pouvant jouer notamment sur la forme de la post-décharge, nous nous sommes intéressés à son utilisation en tant que source plasma pour des applications de traitements de surfaces.Nous avons ainsi étudié des dépôts de films minces de SiOx à partir d’hexaméthyldisiloxane (HMDSO) en utilisant la post-décharge comme source d’oxygène atomique permettant la décomposition du précurseur organosilicié. L’HMDSO est utilisé ici car il est assez simple à manipuler et il a été souvent étudié, nous permettant d’obtenir sur lui de nombreuses informations. Différentes structures auto-organisées sont apparues au sein de ces dépôts et ont été étudiées afin de comprendre leur mécanisme de formation / In order to always go to the smallest, a plasma reactor microwave in resonant cavity operating at atmospheric pressure was developed at the Institut Jean Lamour (IJL, UMR 7198) in the team ESPRITS (Expériences et Simulations des Plasmas Réactifs - Interaction plasma-surface et Traitement des Surfaces).This plasma reactor has the particularity to provide post-discharge of small size (about one millimeter). An Ar-O2 gas is used as the plasma component. The filamentous appearance of this type of plasma is a major feature of the device. Furthermore, the afterglow is notably composed of atomic oxygen, active species such as widely used PECVD or surface functionalization.Our job was to develop the plasma reactor and to characterize the resulting afterglow. After mastering the key parameters that can play on the particular shape of the afterglow, we were interested in its use as a plasma source for surface treatment applications.We studied deposition of SiOx thin films from hexamethyldisiloxane (HMDSO) using post-discharge source of atomic oxygen for the decomposition of the organosilicon precursor. The HMDSO is used here because it is fairly easy to handle and it has often been studied, allowing us to obtain much information on him. Various self-organized structures appeared in these deposits and have been investigated to understand their formation mechanism

L’irradiation des matériaux par des impulsions laser ultrabrèves déclenche un agencement anisotrope de la matière à l’échelle nanométrique: des structures de surface périodiques induites par laser (LIPSS). L'énergie laser déposée et distribuée de manière inhomogène dans le matériau induit des contraintes thermiques locales et des changements de phase transitoires entraînant ainsi des modifications microstructurales. Cette thèse porte sur le rôle de l'altération de la surface irradiée ainsi que les modifications microstructurales en profondeur dans la contribution à la formation des LIPSS, en établissant une corrélation entre l'auto-organisation de la matière et la génération de défauts en tenant en compte de l'orientation cristalline. Comme les LIPSS sont générés au seuil de transition de phase, l’étude de la corrélation avec les défauts induits est alors pertinente. Une étude expérimentale couplée à des simulations de dynamique moléculaire effectuées à l’Université de Virginie suggère que l'altération de surface générée par une irradiation d'échantillons monocristallins de Chrome dans le régime de spallation est susceptible de jouer un rôle majeur dans le déclenchement de génération de LIPSS de haute fréquence spatiale. La microscopie à force atomique ainsi que les résultats de simulations attestent que les caractéristiques de rugosité de surface à l'échelle nanométrique dépendent de l'orientation cristalline. La forte rugosité de surface générée par la première impulsion laser active la diffusion de la lumière laser et l’exaltation du champ local lors des irradiations ultérieures, ce qui génère des structures LIPSS de haute fréquence plus prononcés du côté (100) que celle du (110). Une étude expérimentale approfondie, utilisant la microscopie électronique rétrodiffusés et transmission, a révélé que le Cr (110) est plus susceptible d'être endommagé que les autres orientations cristallines de surface. On constate que les défauts induits par le laser peuvent altérer la topographie de surface et la région sous-jacente, ce qui peut avoir un impact sur les caractéristiques des centres de rugosité favorisant la formation de structures de fréquence spatiale élevée. Afin d’accéder à la transition de phase subie dans la région de formation des LIPSS, une approche d'analyse microstructurale à haute résolution couplée à des calculs hydrodynamiques est utilisée, comprenant la croissance épitaxiale et la nanocavitation. La formation de structures de fréquence spatiale élevée est le résultat de nanocavités périodiques piégés sous la surface, ainsi que des nanocavités apparues à la surface des matériaux cubiques faces centrées.De plus, étant donné que le feedback dans la formation des LIPSS est souvent évoquée, le comportement dynamique des surfaces a été sondé par microscopie électronique à photoémission et étayé par des calculs électromagnétiques. Un caractère périodique des photoélectrons émis par les creux des LIPSS a été mis en évidence, ce qui a permis de vérifier la modulation du dépôt d'énergie.Le travail effectué contribue non seulement à progresser vers l'objectif général d’élucider le phénomène complexe multi-échelles de la formation des LIPSS, mais ouvre une nouvelle voie expérimentale pour générer des structures non conventionnelles avec des périodicités extrêmes (~60nm), offrant ainsi de nouvelles opportunités pour le traitement laser ultrarapide des métaux. / Irradiation of materials by ultrashort laser pulses triggers anisotropically structured arrangement of matter on the nanoscale, the so-called laser-induced periodic surface structures (LIPSS), or ‘ripples’. Ultrashort laser energy deposited and distributed inhomogeneously in the material launches local thermal stresses and transient phase changes yielding microstructural modifications. This thesis focuses on the role of irradiated surface alteration as well as in-depth microstructural modifications in promoting LIPSS formation, by establishing a correlation between self-organization of matter and defect generation taking into account crystalline orientation. Since LIPSS are generated at the threshold of phase transition, then the correlation with defects formation is relevant. An experimental study coupled with molecular dynamic MD simulations performed in the University of Virginia suggest that surface alteration generated by a single pulse irradiation of monocrystalline Cr samples in the spallation regime is likely to play a main role in triggering high-spatial frequency LIPSS generation upon irradiation by multiple laser pulses. Atomic force microscopy as well as computational results suggested that the nanoscale surface features are crystalline orientation dependent. The higher surface roughness generated by the first laser pulse activates scattering of the laser light and the local field enhancement upon irradiation by the second laser pulse, leading to the formation of much more pronounced high-spatial frequency structures on the (100) surface as compared to (110) one. An extended in-depth experimental study, using electron backscattered and transmission microscopy, combined with large-scale two-temperature model TTM-MD simulations revealed that Cr (110) is more likely to get damaged. It is found that laser-induced defects can alter the surface topography and the region beneath it which can impact in turn the roughness center features promoting high-spatial frequency structures formation. In order to infer the phase transition undergone in the LIPSS region, a high resolution microstructural analysis approach coupled with hydrodynamic calculations is employed, including epitaxial regrowth and nanocavitation. High-spatial frequency structures formation is found to be the result of periodic nanovoids trapped beneath the surface as well as nanocavities emerged at the surface on fcc materials. Furthermore, since optical feedback in LIPSS is often evoked, the behavior of dynamical surfaces was probed by photoemission electron microscopy and supported by electromagnetic calculations. A periodic character of photoelectrons emitted from nanoholes was unveiled, which in turn verified a modulated energy deposition. The performed work not only contributes to the progress towards the general goal of untangling the complex multiscale phenomenon of the LIPSS formation, but unlocks a new experimental setup to generate unconventional structures with extreme periodicities (~60 nm), which offers new opportunities in ultrafast laser processing of metals.

This thesis reports on the controlled formation of surface rippling structures induced by tip scanning processes on compliant and brittle materials. Periodic surface structures were generated on polymeric and vitreous materials and with different length scales. Two aspects were focused on: the controlling of orientation and periodicity of the resulting structures via proper tuning the scan conditions and the physical mechanisms ruling the early stages of plowing wear causing the rippling effect. Specifically the influence of the scanned area geometric shape on the orientation of the rippling structure was investigated on a polystyrene surface. Nanoripples were induced by scanning the surface with a silicon tip using atomic force microscopy and dedicated scripts. Inside a structured area two ripple orientations can be observed: near boundaries the ripple orientation is determined by boundary orientation and regions away from the boundaries the ripples are aligned in a steady orientation. This steady orientation can be tuned by the distance between the scan lines. In the boundary regions the orientation of the ripples is different from steady orientation. The orientation of the boundaries clearly affected the orientation of the ripples and the tendency of the ripples to align in a steady angle defined by the scan parameters could be significantly modified. Geometric shapes like squares, circles, stars, pentagons and hearts allowed to distinguish the influence of curved and straight boundaries. Straight boundaries with different orientations allowed a detailed analysis of the influence of the angle on the rippling process. Straight boundaries inclined in the direction of the steady state angle of ripple orientation previously defined generate a uniform ripple pattern covering the entire scan area. The aspect of wear originating from the rippled surface was also investigated on similar polystyrene surfaces. As a result of repetitive scan passes spherical particles with diameters up to 250 nm were nucleated and detached from the surface. The particles originate from the crests of the ripples formed in the first scan pass. As proven by the lateral force signal the detachment occurs smoothly without a static friction peak suggesting a crazing mechanism induced by the scanning tip. Once detached from the surface the particles are displaced and piled up along the edges of scanned area. The formation of periodic surface structures was also investigated on a brittle silica glass. By a combination of scratch tests performed with a diamond microtip mounted in a nanoindenter and imaging with atomic force microscopy the existence of a periodic herringbone pattern inside scratch grooves on silica glass was proven. The rippled pattern was induced in the scratch process when the indenter was pulled laterally along the surface resulting in a microscopic scratch groove. The load was varied up to 30 nN and the scan velocity up to 500 µm/s. The resulting periodicity of the structures was found to increase linearly with increasing scratch velocity. The repetition distance was in the range of sub-µm and the corrugation in the range of a few hundred nm, which was well below indentation depth. In both cases, the surface rippling on a polymeric surfaces and the formation of a periodic pattern inside microscratches on a glass surface, the results were found to be consistent with minimalistic theoretical models for stick-slip.:Contents i Abstract iii Zusammenfassung v 1. Introduction 1 1.1. Periodic surface structures – relevance and formation 1 1.2. Surface rippling created by scanning probe lithography 2 1.3. Wear and nanoparticle release 4 1.4. Aim and outline 4 2. Experimental methods and fundamental concepts 6 2.1. Nanolithography 6 2.2. Atomic force microscopy 7 2.3. Nanoindentation and -scratching 10 2.4. Wear 11 2.5. Stick-slip motion 12 2.6. Spin coating 14 3. Surface rippling on polystyrene 15 3.1. Background and motivation 15 3.2. Methods 20 3.2.1. Sample preparation 20 3.2.2. Scanning probe lithography process 20 3.2.3. Imaging of structures and nanoparticles 21 3.3. Effect of boundaries on the orientation of surface rippling 22 3.4. Particle release as a result of surface rippling 31 4. Periodic structures inside scratches on silica glass 37 4.1. Background and motivation 37 4.2. Methods 38 4.2.1. Sample preparation 39 4.2.2. Scratch tests 39 4.2.3. AFM imaging and analysis 39 4.3. Surface rippling induces by scraping with a sharp indenter 40 5. Conclusion and outlook 49 A. Appendix surface rippling on polymers I B. Appendix surface rippling on glass IV Acknowledgements VII References IX