The class of models which is studied in this paper, multi-unit longitudinal models, combines both the cross-sectional and the longitudinal aspects of observations. Many empirical investigations involve the analysis of data structures that are both cross-sectional (observations are taken on several units at a specific time period or at a specific location) and longitudinal (observations on the same unit are taken over time or space). Multi-unit longitudinal data structures arise in economics and business where panels of subjects are studied over time, biostatistics where groups of patients on different treatments are observed over time, and in situations where data are taken over time and space. Modelling issues in multi-unit longitudinal models with random coefficients and patterned correlation structure are illustrated in the context of two data sets. The first data set deals with short time series data on annual death rates and alcohol consumption for twenty-five European countries. The second data set deals with glaceologic time series data on snow temperature at 14 different locations within a small glacier in the Austrian Alps. A practical model building approach, consisting of model specification, estimation, and diagnostic checking, is outlined. (author's abstract) / Series: Forschungsberichte / Institut für Statistik

A novel localized surface plasmon resonance (LSPR) sensor that differentiates between background refractive index changes and surface-binding of a target analyte (e.g. a target molecule, protein, or bacterium) is presented. Standard, single channel LSPR sensors cannot differentiate these two effects as their design allows only one mode to be coupled. This novel technique uses two surface plasmon modes to simultaneously measure surface binding and solution refractive index changes. This increases the sensitivity of the sensor. Different channels or modes can be created in sensors with the introduction of gold nanospheres or gold nanorods that act as receptor mechanisms. Once immobilization was achieved on gold nanospheres, the technique was optimized to achieve the same immobilization for gold nanorods to get the expected dual mode spectrum. Intricate fabrication methods are illustrated with using chemically terminated self assembled monolayers. Then the fabrication process advances from chemically silanized nanoparticles, on to specific and systematic patterns generated with the use of Electron Beam Lithography. Comparisons are made within the different methods used, and guidelines are set to create possible room for improvement. Some methods implemented failed, but there was a lot to learn from these unsuccessful outcomes. Finally, the applications of the dual mode sensor are introduced, and current venues where the sensors can be used in chemical and biological settings are discussed.

This dissertation is focused on the interaction between femtosecond laser and patterned two-dimensional gold nanostructures. The sample was prepared by two different lithographic techniques, the nanosphere lithography and the electron beam lithography. Characterization was carried out with scanning electron microscopy, transmission electron microscopy, atomic force microscopy, and UV-vis absorption spectroscopy. Femtosecond transient absorption spectroscopy was used to answer a number of fundamental questions regarding the laser-nanostructure interaction. Under a low density irradiation of a femtosecond laser, we examined the effect of the lattice crystallinity on the electron-phonon relaxation in monolayer periodic array nanoparticles prepared with nanosphere lithography. We found that the electron-phonon relaxation rate was faster in polycrystalline nanoparticles and decreases greatly in single crystalline nanospheres, which is explained by the presence of high density grain boundaries. The ultrafast laser-induced coherent phonon oscillations in patterned gold nanoparticles are also fully characterized. We studied the effect of size, shape, thickness, monitoring wavelength, and materials of the prismatic array nanoparticles on the period of their coherent phonon oscillations. In a gold nanodisk pair system, we found that the fractional change in the vibration frequency increases exponentially with decreasing the ratio of the interparticle separation to the particle diameter, which is explained by the coupling of the induced electric field in one nanodisk by the strong surface plasmon field of its pair partner. Based on the coherent phonon oscillation of gold caps on a polystyrene sphere monolayer array, a new all-optical gigahertz modulation technique is developed. Under a high density irradiation of a femtosecond laser, the melting and ablation processes can be induced in gold nanoparticles. We studied femtosecond laser induced shape and localized surface plasmon resonance band changes of gold prismatic array nanoparticles. We also observed that the femtosecond laser irradiation of the nanoprisms at the surface plasmon resonance absorption maximum can cause them to detach from the substrate and 'fly away'. Atomic force microscopy and scanning electron microscopy measurements revealed that the displaced nanoparticles are thinner and smaller than the undisplaced ones, which supports an atomic ablation mechanism.

Accompanying workbook not available in digital format / Both empirical and anecdotal evidence indicates that visual communication1 design practices implemented by designers with full colour vision often disadvantage, and sometimes endanger, colour-blind people. The thesis The Machine postulates that colour-blind people – comprising approximately 8% of males and 0.5% of females (Lewis et al., 1990) – are marginalized by such practices. It argues that this group could benefit from a design strategy that enhances the communicative potential and visibility of colour. The proposed strategy involves embedding pattern into potentially confusing colours such as red and green. The embedded pattern would function for colour-blind people as an additional clue to the identity of these colours. The thesis contends that while colour alone can be confusing for colour-blind people, patterned colour could offer a solution with a wide range of possible applications. The research aims of The Machine include: developing a system of patterned colour; creating a wordless picture book that demonstrates the effectiveness of the system; constructing a narrative around the condition of red-green colourblindness; and employing visual rhetoric2 to increase awareness of and sensitivity to colour-blindness among those with full colour vision. The design of the thesis is supported by research in a number of interrelated areas. These include the history of pattern post-1850, particularly in Western culture; precedents for patterned colour; and visual rhetoric in story-telling. The research also incorporates an analysis of the defining characteristics of ten late twentieth-century and early twenty-first-century wordless picture books. The thesis is further supported by applied research into patterned colour and visual rhetoric. The Machine aims to benefit colour-blind people, a significant minority group whose visual needs are currently inadequately met. In addition, it proposes broadening the cultural role and significance of pattern. Moreover, by incorporating informative elements usually associated with pedagogic material, it aspires to extend the boundaries of the fantasy picture book genre. 1 Visual communication (n): communication that relies on vision (Wordnet, 2006). 2 Visual rhetoric: the use of visual techniques, such as the creation of visually ‘engaging’ characters, as a means of persuading a target audience

A l'échelle nanométrique, les solides peuvent changer de forme par diffusion de surface, et présentent alors des propriétés de mouillage qui s'apparentent à celles des liquides. Dans cette thèse, nous nous sommes plus particulièrement intéressés au comportement de mouillage des nano-solides sur des substrats nanopatternés, comportant par exemple des piliers ou des tranchées. Sur ces substrats, les nanoparticules (ou ilots) solides peuvent être multi-stables : c'est-à-dire qu'ils peuvent présenter plus d'un état localement stable. Comme les liquides, les solides ont été observés par exemple dans des états dits de Wenzel (pénétrant dans la structure du substrat) ou de Cassie-Baxter (ne pénétrant pas). Grâce à une combinaison de simulations Monte Carlo Cinétiques et de modèles analytiques, nous avons étudié la stabilité de ces états et leur dynamique de transition. Plus particulièrement, avons mis en évidence le rôle de la diffusion de surface et de la nucléation bidimensionnelle sur la dynamique de transition. Nous avons aussi montré que les contraintes élastiques augmentent la stabilité des états de Cassie-Baxter, et mènent à de nouveaux états, avec des morphologies asymétriques ou partiellement empalées dans les nanostructures. Finalement, nous avons proposé de contrôler les transitions de mouillage à l'aide de l'électromigration induite par un faisceau d'électrons. Nos résultats ouvrent la voie vers une nouvelle direction pour les investigations expérimentales / At the nanometer scale, solids can change shape thanks to surface diffusion and therefore display wetting properties that can be likened to those of liquids. This doctoral thesis intends to study particularly the wetting behaviour of nano-solids located on nanopatterned substrates, containing for instance pillars or trenches. Upon these substrates, solid nanoparticles (or islands) can be multi-stable – that is to say they can display more than one locally-stable state. Just like liquids, solids have been observed for example in the context of the so-called Wenzel state (penetrating the very structure of the substrate) and Cassie-Baster state (no penetration). By combining Kinetic Monte Carlo simulations with analytical models, we conducted a study on the stability of these states along with their dynamics of transition. In particular, we highlighted the specific roles that surface diffusion and bidimensional nucleation play in regards to the dynamics of transition. We also demonstrated that elastic constraints increase the stability of Cassie-Baxter states and lead to new states, with either asymmetric morphologies or morphologies that are partially impaled into the nanostructures. Last but not least, we proposed to control wetting transitions using the electromigration brought on by an electron beam. Our results pave the way for a new direction in the field of experimental investigations

Quantum dots (QDs) are a semiconductor nanostructure in which a small island of one type of semiconductor material is contained within a larger bulk of a different one. These structure are interesting for a wide range of applications, including highly efficient LASERs, high-density novel memory devices, quantum computing and more. In order to understand the nature of QDs, electrical characterisation techniques such as capacitance-voltage (CV) profiling and deep-level transient spectroscopy (DLTS) are used to probe the nature of the carrier capture and emission processes. This is limited, however, by the nature of QD formation which results in a spread of sizes which directly affects the energy structure of the QDs. In this work, I sought to overcome this by using Si substrates patterned with a focused ion beam (FIB) to grow an array of identically-sized Ge dots. Although I was ultimately unsuccessful, I feel this approach has great merit for future applications.In addition, this thesis describes several unusual characteristics observed in InAs QDs in a GaAs bulk (grown by molecular beam epitaxy-MBE). Using conventional and Laplace DLTS, I have been able to isolate a single emission transient. I further show an inverted relation between the emission rate and the temperature under high field (emissions increase at lower temperatures). I attribute this to a rapid capture to and emission from excited states in the QD. In addition, I examine a metastable charging effect that results from the application of a sustained reverse bias and decreases the apparent emission rate from the dots. I believe this to be the result of a GaAs defect with a metastable state which acts as a screen, inhibiting emission from the dots due to an accumulation of charge in the metastable state. These unusual characteristics of QDs require further intensive work to fully understand. In this work I have sought to describe the phenomena fully and to provide hypotheses as to their origin.

Sorted patterned ground are a group of periglacial microforms which create more or less symmetrical forms due to frost action and especially repeated freeze-thaw cycles. The origin of sorted patterned ground in the Giant Mts. is presumed in late Pleistocene and they are suggested to be recently inactive (with the exception of sorted circles). Their occurrence is linked to the topmost localities with flat surfaces and intense wind action which causes low snow cover and allow deep soil freezing. The submitted diploma thesis deals with the influence of site characteristics (such as microclimatic extremity, terrain morphology and lithology) on morphology and sorting degree of sorted patterned ground. Field research was carried out along a transect tracing the microclimatic extremity gradient (represented by altitude and so-called relative snow height) in area of Mt. Luční hora in the eastern part of the Giant Mts. which in relatively homogeneous from the viewpoint of lithology and wind exposure. The transect was further extended across the Modré sedlo Saddle to the Mt. Studniční hora where there also occur various types of fossil sorted patterned ground or quasi- active sorted circles in the Modré sedlo Saddle, respectively. However, there is a variability of lithological as well as altitude...

Les surfaces texturées sont devenues, ces dernières années, des substrats de choix pour de nombreuses applications. En effet, la texturation des surfaces, de l'échelle nanométrique à l'échelle microscopique, permet d'accroître les propriétés d'adhérence ou de renforcer la résistance mécanique intrinsèque. Dans ce travail de thèse nous proposons une étude sur l'influence des textures chimiques sur le comportement tribologique, adhésif et sur la mouillabilité des substrats. Dans le premier chapitre, on propose une stratégie de micro-texturation des surfaces basées sur la technique de microcontact-printing et le greffage de chaînes de polymères de géométries/formes contrôlées. En outre, on a notamment étudié de manière approfondie la mouillabilité des surfaces texturées afin de comprendre les effets de diminution de taille des textures sur le comportement adhésif. Dans les expériences d'adhésion et frottement, un dispositif de type JKR (pour Johnson, Kendall et Roberts), une machine de frottement et une FFM ont été utilisés permettant d'observer le contact entre une sphère élastique et une pointe rigide avec un plan texturé tout en contrôlant la force entre les surfaces. En outre l'utilisation de ces différentes approches ne nous a pas finalement donné des explications satisfaisantes sur les mécanismes agissant sur les phénomènes interfaciaux. De ce fait, l'utilisation du démouillage de films minces de PS et de PDMS sur des surfaces texturées nous as permis de suivre l'évolution de l'instabilité du bourrelet à l'interface. Enfin, dans le dernier chapitre, nous avons étudier les différents aspects prédominants des phénomènes interfaciaux sur des surfaces homogènes / Micro and Nanoscale surface patterns are considered as potential templates and building blocks for Micro/nanotechnology. As for materials in general, these micro /nano-scale surface structures have been of increasing research interest in recent years, due to their unique properties. They are expected to exhibit novel and significantly improved physical, chemical, mechanical and other properties, as well as to offer opportunities for manifestation of new phenomena and processes. In the present PhD work, we propose a multiple scale analysis of the adhesion, friction and wetting behaviors for different patterned interfaces. In a first chapter, we developed a general methodology to design well-defined surfaces combining micro-contact printing (µCP), self-assembled monolayers (SAMs) and polymer grafting techniques. Then we study the wettability of a patterned solid surface. Where, the stick-slip regime, and the effect of the patterning at the mesoscale was investigated. Furthermore, we concentrate on the dependence of adhesion and friction between a polymer and a rigid tip on the composition of the patterned substrates using a JKR, FFM and friction machines. Intriguingly, the uses of these approaches did not provide us with a clear answer to our bewilderment. Therefore, in the third chapter, we adopted the approach of the dewetting of thin polymer film on top of patterned surfaces. We study the impact of the solid/liquid boundary condition on the evolution of the rim instability during the course of dewetting. The last chapter details the investigation of the predominant aspect between the chemistry introduced on the surface and the mechanical proprieties of the substrate

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