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

Ein zentraler Nachteil der meisten Koordinationspolymere ist, dass sie elektrische Isolatoren sind. In dieser Arbeit wurden konjugierte Koordinationspolymere auf ihre Leitfähigkeit untersucht, die eine Rhodium-Paddle-Wheel-Struktur besitzen. Die Beschichtung auf einer funktionalisierten Oberfläche im Vorfeld der C-AFM-Messung wurde mittels eines selbstgebauten Dip-Coaters realisiert. Koordinationspolymere, die das [Rh2(ac)4]-Paddle-Wheel enthalten, sind unabhängig von den untersuchten Linkern Isolatoren. Werden die Acetatliganden mit drei oder vier Acetamidatliganden ausgetauscht, so ist das entstandene Koordinationspolymer leitfähig. Temperaturabhängige C-AFM-Messungen ergeben eine für hohe Feldstärken konstante Aktivierungsenergie, die je nach Koordinationspolymer zwischen 0,3 eV und 0,7 eV beträgt. Anhand der Ergebnisse wurde gezeigt, dass der Ladungstransport durch einen Hopping Mechanismus dominiert wird. C-AFM ist eine aussagekräftige Methode zur Charakterisierung leitfähiger Koordinationspolymere auf der Oberfläche.

This understanding of nanocellulose can be directly applied in future formulation design to use nanocellulose in polymer nanocomposites, foams, emulsions, latexes, gels and biomedical materials. / In this study, the potential of nanocellulose as a reinforcing agent in composite materials was investigated using atomic force microscopy (AFM). AFM was used to probe the mechanical properties of nanocelluloses and to investigate their interactions and adhesion in liquid media. Amplitude modulated-frequency modulated AFM was used to map the mechanical properties of cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs). Results showed Young’s moduli of 90 GPa and 120 GPa for CNCs and CNFs, respectively, which are comparable to literature values determined using other methods. Additionally, colloid probe AFM was implemented to observe the interactions (attractive, repulsive, steric, adhesive) between cellulose and silica colloid probes with anionic CNCs (containing either a Na+ or H+ counterion) and cationic CNCs. Colloid probe AFM measurements were carried out in five different liquid media: two salt solutions (NaCl and CaCl2) and three surfactant solutions (cationic cetyltrimethylammonium bromide, CTAB; anionic sodium dodecyl sulfate, SDS; and nonionic Triton X100). It was found that low salt concentrations resulted in electrostatic repulsion and high adhesion, whereas the reverse was observed at high salt concentrations. On the contrary, an increased surfactant concentration and increased number of surfactant aggregates (micelles, bilayers, etc.) resulted in increased adhesion. Surprisingly, the interactions were strongly dependent on the CNC counterion as surfactant adsorption seemed to be primarily driven by electrostatic interactions; CTAB adsorbed more to anionic CNCs, SDS adsorbed more to cationic CNCs and Triton X100 adsorbed minimally to all CNCs. Electrophoretic mobility and particle size data showed complementary results to colloid probe AFM, indicating that interactions between surfactants and CNC films and CNCs in suspension are closely related. This research suggests that CNCs have potential as reinforcing agents due to their high strength and the tunability of their interactions through the simple addition of salts or surfactants. This understanding can be directly applied in future formulation design to use nanocellulose in polymer nanocomposites, foams, emulsions, latexes, gels and biomedical materials. / Thesis / Master of Applied Science (MASc) / Nanocellulose is a sustainable nanomaterial most commonly extracted from plants and trees. In recent research, nanocellulose has been shown to have potential as a reinforcing agent for materials such as plastics, foams, paints and adhesives. In this study, the potential of nanocellulose was investigated using atomic force microscopy (AFM). As predicted, AFM measurements indicated that nanocellulose has a high stiffness, supporting the substitution of this biobased material in the place of metals and synthetic fibres. AFM was also used to examine particle interactions in salt and soap-like (surfactant) solutions; changes in nanocellulose size and charge were used to support the findings. Negatively charged nanocellulose interacted more with positively charged surfactants and vice versa. Low salt and high surfactant concentrations led to high adhesion and better material compatibility, which is preferred. This understanding can help us design better nanocellulose materials for future applications.

Perovskit solceller (PSCs) är kända som 'ljusomvandling' enheter med ökad omvandlingseffektivitiet (PCE). PSCs är kända för detta flexibilitet och hög tolerans mot defekter och består av fem lager med olika material och egenskaper. De fem lagren är följande; transparant elektrod, elektron ledande lager (ETL), perovskit lager, hål ledande lager (HTL) och metallelektroden.  Detta forskningsarbete fokuserar på metallelektroden (Cu-tunn film), HTL (CuI-tunn film) och det aktiva lagret (CuI-komplex).  Syftet med denna studie är att undersöka effekten av olika tjocklekar på ytans morfologi och grovhet för att se mängden jod som tränger sig genom filmen genom att beräkna volymen.  Resultatet av denna studie visar att ökad tjocklek leder till ökad grovhet. Man ser även att en ökad tjocklek leder till ett mer homogent och jämn yta, och dessutom ökar kornstorleken, vilket tyder på att kvaliten av kristallisationen förbättras.  Slutligen, genom att känna till tjockleken och storleken (arean) på ytan av proverna kunde man beräkna volymen för att indikera mängden jod som trängt sig genom filmen. Resultatet av denna del indikerade att ju tjockare provet är, desto mer kommer jod att tränga sig genom filmen. / Perovskite solar cells (PSCs) are known as light-harvesting devices with increased power conversion efficiencies (PCE). PSCs are known for their flexibility and high tolerance towards defects. It consists of five different layers with different materials and functions. Transparent electrode, electron transport layer (ETL) , perovskite or active layer , hole transport layer (HTL) and metallic electrode. In this research project, the focus is directed towards the metallic electrode (Cu-thin film), hole transport layer (CuI-thin film) and the active layer (CuI-complex). The purpose of this study is to investigate the effect of different thicknesses on the surface morphology and roughness and to see how much iodine is diffusing through the film by calculating the volume.  The results of this project present that the increase in thickness leads to an increase in roughness. It also shows that an increase in thickness leads to a more homogeneous and uniform surface and in addition the grain size increases which indicates that the quality of crystallization improves. Finally, by knowing the thickness and surface area of the samples the volume was calculated to indicate how much iodine is diffusing through the film and the results for this part indicated that the thicker the sample, more iodine will diffuse through the film.

Cette étude vise à définir l'effet des lipoprotéines de basses densité natives (LDL) et oxydées (ox-LDL) sur les fonctions des cellules endothéliales en relation avec les processus physiopathologiques de l'athérosclérose. Le microscope à force atomique (AFM) fut utilisé en combinaison avec les méthodes biochimiques traditionnelles afin d'acquérir de l'information sur les propriétés biomécaniques des cellules endothéliales. L'AFM est un outil permettant l'acquisition d'images et de mesures de forces quantitatives concernant les propriétés viscoélastiques des cellules vivantes selon leur exposition aux LDL ou ox-LDL. L'AFM rassemble localement des informations sur la membrane cellulaire et le cytosquelette des cellules et ce, de manière non invasive. Il est ensuite possible de corréler les résultats obtenus avec les marquages immunohistochimiques afin d'évaluer la réponse cellulaire suite à une exposition à des LDL ou ox-LDL. Ces données recueillies, les protocoles étant au point, il ne restera plus qu'à effectuer les tests avec les antioxydants afin de déterminer les agents et les dosages appropriés permettant une protection salutaire de l'endothélium. Ce travail amène donc de nouvelles connaissances sur les mécanismes moléculaires fondamentaux de la dysfonction endothéliale en vue éventuellement de développer de nouvelles thérapies cytoprotectrices efficaces. Une méthode d'imagerie des LDL a également été mise au point en utilisant l'AFM. Il est maintenant possible d'obtenir des images de bonne qualité permettant aussi de mesurer les dimensions de LDL individuelles. Cette technique pourrait entre autre servir à évaluer des pathologies touchant les LDL comme le diabète.

Solid oxide fuel cells (SOFCs) represent a next generation energy source with high energy conversion efficiency, low pollutant emission, good flexibility with a wide variety of fuels, and excellent modularity suitable for distributed power generation. As an electrochemical energy conversion device, SOFC’s performance and reliability depend sensitively on the catalytic activity and stability of the electrode materials. To date, however, the development of electrode materials and microstructures is still based largely on trial-and-error methods because of inadequate understanding of the mechanisms of the electrode processes. Identifying key descriptors/properties of electrode materials or functional heterogeneous interfaces, especially under in situ conditions, may provide guidance to the design of electrode materials and microstructures. This thesis aims to gain insight into the electrochemical and catalytic processes occurring on the electrode surfaces using unique characterization tools with superior sensitivity, high spatial resolution, and excellent surface specificity applicable under in situ/operando conditions. Carbon deposition on nickel-based anodes is investigated with in situ Raman spectroscopy and SERS. Analysis shows a rapid nucleation of carbon deposition upon exposure to small amount of propane. Such nucleation process is sensitive to the presence of surface coating (e.g., GDC) and the concentration of steam. In particular, operando analysis of the Ni-YSZ boundary indicates special function of the interface for coking initiation and reformation. The coking-resistant catalysts (BaO, BZY, and BZCYYb) are systematically studied using in situ Raman spectroscopy, SERS, and EFM. In particular, time-resolved Raman analysis of the surface functional groups (-OH, -CO3, and adsorbed carbon) upon exposure to different gas atmospheres provides insight into the mechanisms related to carbon removal. The morphology and distribution of early stage carbon deposition are investigated with EFM, and the impact of BaO surface modification is evaluated. The surface species formed as a result of sulfur poisoning on nickel-based anode are examined with SERS. To identify the key factors responsible for sulfur tolerance, model cells with welldefined electrode-electrolyte interfaces are systematically studied. The Ni-BZCYYb interface exhibits superior sulfur tolerance. The oxygen reduction kinetics on LSCF, a typical cathode material of SOFC, is studied using model cells with patterned electrodes. The polarization behaviors of these micro- electrodes, as probed using a micro-probe impedance spectroscopy system, were correlated with the systematically varied geometries of the electrodes to identify the dominant paths for oxygen reduction under different electrode configurations. Effects of different catalyst modifications are also evaluated to gain insight into the mechanisms that enhance oxygen reduction activity. The causes of performance degradation of LSCF cathodes over long term operation are investigated using SERS. Spectral features are correlated with the formation of surface contamination upon the exposure to air containing Cr vapor, H2O, and CO2. Degradation in cathode performance occurs under normal operating conditions due to the poisoning effect of Cr from the interconnect between cells and the high operating temperature. The surface-modified LSCF cathode resists surface reactions with Cr vapor that impairs electrode performance, suggesting promising ways to mitigate performance degradation.

The electroplating industries use soluble nickel salts in numerous applications. Over the past few years this has become problematic due to the reclassification of these salts from a harmful substance to now a toxic substance. The introduction of the legislation REACH (Registration, Evaluation, Authorisation & restriction of CHemicals) has meant the electroplating industry has had to use less harmful chemicals where possible, thus meaning companies are investing in research to find an alternative to the nickel deposit. In this study, alternative deposits under investigation as a potential replacement to the nickel deposit under the decorative chromium deposit has been characterised in terms of the appearance, surface topography and corrosion resistance by using spectrophotometry, scanning electron microscopy (SEM), atomic force microscopy (AFM), linear polarisation, electrochemical impedance spectroscopy (EIS) and accelerated corrosion salt spray methods. Spectrophotometry identified that a white Cu-Sn alloy gave a bluer appearance in comparison to the nickel deposit, when the chromium deposit was plated on top this modified the colour slightly giving the white Cu-Sn alloy with chromium a similar appearance to the nickel and chromium deposit. The yellow Cu-Sn alloy was yellow in colour with a visibly dull appearance, but when chromium was plated on top of the yellow Cu-Sn alloy the colour was improved but still remained dull. The SEM and AFM results identified that the white Cu-Sn alloy deposit had similar nodulated topography to the nickel deposit and when the chromium was plated on top the topography changed only slightly. While the yellow Cu-Sn alloy deposits showed a more crystalline structure and increased roughness in comparison to the nickel deposit, the chromium deposit plated on top did not change the structure of the underlying deposit but it did reduce the roughness slightly. Electrochemical corrosion tests showed the white Cu-Sn alloy to have a higher polarisation resistance compared to the nickel deposit, thus suggesting it would provide similar corrosion protection to the nickel deposit. The yellow Cu-Sn alloy proved to have a faster corrosion rate in comparison to the nickel deposit. Accelerated corrosion tests proved the white Cu-Sn alloy to be more corrosive than the nickel despite the electrochemical test results, it was concluded that the white Cu-Sn alloy deposit was porous and therefore provided less corrosion protection to the substrate in comparison to the nickel deposit. The yellow Cu-Sn alloy had a lower corrosion protection than the nickel deposit and when combined as a duplex Cu-Sn alloy with the white Cu-Sn alloy deposit there was no improvement in corrosion performance. The plated chromium deposit did improve the corrosion protection for most deposits but none of the alternatives could match the corrosion protection offered by the standard nickel with chromium deposit. This study concluded that the white Cu-Sn alloy with chromium deposit was found to be a potential alternative to the nickel with chromium deposit for applications where appearance is primary, no alternative could be found to match the corrosion protection provided by the standard nickel and chromium process.

This dissertation serves to study a protein's conformation-function relationship since immobilized proteins often behave differently from their solution-state counterparts. Therefore, this study is important to the application of protein-based biodevices. Another aim of this dissertation is to explore a new approach to realize low voltage electrowetting without the help of oil bath. Utilizing this approach, a protein micro-separation was realized. Additionally, the interfacial properties of ionic liquid (IL) solid-like layer, which played a key role in electrowetting, was studied for further developments of IL-based applications. Atomic Force Microscopy (AFM) was utilized in the study and played multiple roles in this dissertation. First, AFM was used as a fabrication tool. In the contact mode, conductive AFM tip was used to conduct the electrochemical oxidation to create a chemical pattern or to conduct an electrowetting experiment. Subsequently, AFM was used as a characterization tool in the tapping mode to characterize the surface structure, the thickness, and the surface potential. Furthermore, AFM in the contact mode was used as a measurement tool to measure the tribological force properties of sample. The results of the study concerning the conformational change in immobilized calmodulin showed that the immobilized CaM retained its activity. Additionally, the immobilization of CaM on a solid support did not interfere with the ability of the protein to bind calcium, as well as CaM kinase binding domain. For the electrowetting experiment, our data suggested that the ultra-high capacitance density of the IL dielectric layer leads to the low voltage electrowetting. We also successfully demonstrated the streptavidin and GFP proteins separation by Electrowetting-on-Dielectric (EWOD) force. The results of the surface properties study indicated that the charge and dipole of the substrate can influence the structures and properties of the IL interfacial layer. Our study would be beneficial in research and assay work involving engineered proteins, as well as the study and development of electrowetting applications.

Les Imogolites (OH)3Al2O3Si(OH) sont des minéraux naturels découverts en 1962 dans des sols volcaniques japonais qui présentent une structure analogue à celle des nanotubes de carbone. Leur synthèse, décrite depuis 1977, permet l'obtention de tubes bien calibrés et monodisperses. La récente mise en évidence de la possibilité de synthétiser des analogues au germanium en grande quantité en a fait un matériau de choix dans le cadre de mon sujet de thèse visant à préparer des matériaux mésoporeux à base de nanoparticules anisotropes. Lors de la caractérisation de ces imogolites par diffusion de rayons X aux petits angles (SAXS) et microscopie électronique en transmission (MET) et à force atomique (AFM), nous avons montré que ces analogues d'Imogolite sont bien des nanotubes, mais qu'ils existent sous deux formes : des tubes à paroi unique mais également des tubes à paroi double jamais observés à ce jour. La concentration importante utilisée pour cette synthèse a également permis de mieux définir l'espèce précurseur de ces nanotubes appelée proto-imogolite et mal connue jusqu'ici. Après une identification du paramètre déterminant la formation de l'une ou l'autre des structures, nous avons étudié en détail le mécanisme et la cinétique de croissance de ces imogolites. Enfin, des premiers tests sur l'organisation de ces nanotubes en forte concentration ou au sein de microgouttes permettent d'observer leur tendance à s'organiser, propriété prometteuse pour le développement futur d'applications.

Le but de cette thèse était tout d'abord d'étudier les théories physiques qui décrivent la dynamique des polymères à l'échelle macroscopique. Le modèle de Rouse et la théorie d'enchevêtrement de P-G. de Gennes décrivent la dynamique des polymères non enchevêtrés et enchevêtrés, respectivement. Nous avons étudié les différentes transitions entre ces deux régimes en utilisant deux techniques expérimentales : Spéctroscopie dielectrique large bande et rhéologie. Un test complet du modèle de Rouse à été effectué en comparant les prédictions de ce modèle pour la dépendance en fréquence de la permittivité diélectrique et du module de cisaillement aux données expérimentales. Les effets d'enchevêtrement sur les spectres diélectriques ont été discutés. Nous avons ensuite développé des méthodes basées sur la microscopie à force électrostatique afin d'étudier les propriétés diélectriques locales. En utilisant une simulation numérique basée sur la Méthode des Charges Equivalentes, nous avons quantifié la constante diélectrique à partir de la mesure du gradient de force crée par un potentiel statique entre une pointe et un diélectrique. Cette méthode permet d'imager la constante diélectrique avec une résolution spatial de 40 nm. Le retard de phase de la composante en 2 omega de la force ou du gradient de force crée par un voltage alternatif est relié aux pertes diélectriques. Nous avons développé un mode d'imagerie des pertes diélectriques. Cette méthode simple pourrait être appliqué en biologie ou matière molle en générale afin d'étudier des variations locales de constantes dielectriques.