The major part of my dissertation consists of thin films deposited using atomic layer deposition on flat and powder substrates. It details the various optimization experiments for process parameters like dose time, purge time, temperature, and pressure on silicon shards and powder substrates. Spectroscopic ellipsometry (SE) was used to characterize these films over a wide wavelength range (191-1688 nm). An optical model with a BEMA (Bruggeman effective medium approximation) layer was used to fit the ellipsometric data to investigate the optical properties of the alumina surface. The optimized process parameters on the flat surfaces were used for coating powder substrates. I propose a set of experiments to optimize the conditions for coating of powders and high aspect ratio structures by atomic layer deposition (ALD). The coated powders were analyzed by surface analytical techniques like X-ray photoelectron spectroscopy, spectroscopic ellipsometry, transmission electron microscopy, energy X-ray dispersive spectroscopy (EDAX), and BET. The first chapter introduces the technique of atomic layer deposition, and details its advantages and limitations over conventional thin film deposition techniques like chemical vapor deposition and physical vapor deposition. The second chapter details the initial deposition experiments performed on flat surfaces and characterization of thin films using surface analytical tools. I conducted multi-sample analysis on eleven different thin films for calculation of optical constants of alumina. The third chapter introduces thin film deposition experiments performed on powder substrates, several challenges associated with achieving conformal thin films and characterization. The fourth chapter details the experiments to achieve unilateral ALD achieved on one side of the substrates. The fifth chapter details various unconventional materials including liquid water, Coca-Cola, a coffee bean, nitrogen gas, human tooth, and printed office paper, which were analyzed by near ambient pressure XPS (NAP-XPS). This dissertation contains appendices of other tutorial articles I wrote on obtaining optical constants liquid samples using spectroscopic ellipsometry, and good experimental techniques for maintenance of vacuum equipment.

The master´s thesis deals with the study of optical properties of thin transparent layers on the organic materials (PPV, P3HT, TiO2, DPP) and especially with the determination of dispersion dependences of refractive index of prepared thin layers. In the theoretical part there are described principles of deposition thin layers of the analyzed materials and their properties. In addition, there are also described methods of optical properties measurements (optical and interference microscopy and ellipsometry). The combination of interference microscope with digital camera was used for determination of refractive index. The image analysis was used for the determination of parameters (with help of the software HarFA). The images of thin layers surfaces were analyzed from the side of the metal contact as well as from the side of glass. In conclusion, there are presented results of the refractive index of the thin layers obtained from the measured values.

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Ultra-thin films (UTFs) are important in many applications, seen in the semiconductor industry, in chromatography, in sensing, in microfluidics, in aerospace, and in robotics. They also protect materials from corrosion, change surface energies, limit water intrusion into materials, allow material self-cleaning and self-healing, provide scratch resistance, and impart other specific chemical properties. In many cases, UTFs drastically alter surface properties and therefore their applications. It is imperative that proper and consistent characterization be performed on coatings to confirm and understand their desired properties. In Chapter two, Al oxidation under MgF2 protective layers is studied using real time X-ray photoelectron spectroscopy (XPS), and spectroscopic ellipsometry (SE). These tools allowed me to monitor Al oxidation for both short (hours) and long (months) periods of time. XPS revealed the chemical changes that took place in these materials as a function of time, and these changes were verified with SE. These studies help increase an understanding of aluminum changes under MgF2 protective layers. The third chapter demonstrates ab initio calculations guided X-ray photoelectron spectroscopy (XPS) analysis of surfaces functionalized with fluorinated silanes. This study addresses deficiencies in the literature where CF2:CF3 ratios from experimental XPS data do not match theoretical CF2:CF3 ratios. In a systematic approach, I developed semi-empirical models directed both by ab initio calculations and adjustable, empirical parameters. These models were effective in describing the raw data and exceeded fitting methods used in literature. In Chapter four, SiO2 UTFs with variable thicknesses deposited on Eagle XG® glass substrates are characterized. Challenges associated with this work consisted of similar optical functions of the film and substrate as well as backside reflections from the substrate. These obstacles were met using a multi-sample analysis (MSA), a variable angle spectroscopic ellipsometric approach, and mechanical abrasion/roughening of the substrate backside. With these approaches, I developed a model that precisely fit the data collected from all the samples and gave the correct optical function of the material along with thickness values for each film. Surface characterization represents a commitment of resources. It takes time to make measurements, and it takes time to analyze and understand the results. As presented in this work, I increase understanding of ultra-thin films at interfaces using both a multi-tool approach as well as using multiple analytical methods on data collected from each tool.

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With reference to some figures reproduced in this thesis: "Readers may view, browse, and/or download material for temporary copying purposes only, provided these uses are for noncommercial personal purposes. Except as provided by law, this material may not be further reproduced, distributed, transmitted, modified, adapted, performed, displayed, published, or sold in whole or part, without prior written permission from the American Physical Society." / We report on the growth and characterization of strontium ruthenate (214) (Sr2RuO4) and strontium rhodate (214) (Sr2RhO4) in efforts to test their agreement with Landau-Fermi liquid theory using optical measurements. We begin by reviewing the theory of Landau-Fermi liquids and the frequency and temperature dependent conductivities. We review existing work on both Sr2RuO4 and Sr2RhO4 including evidence of agreement with Landau-Fermi liquid theory. We also describe optical floating zone crystal growth and the exact procedures we used to prepare samples of both Sr2RuO4 and Sr2RhO4 via optical floating zone. The resulting Sr2RuO4 crystals were characterized using AC susceptibility measurements and Sr2RhO4 by powder diffraction, single crystal diffraction, and SQUID magnetization measurements. Finally, early optical reflectivity measurements at low temperatures are presented. / Thesis / Master of Science (MSc) / Crystals of Sr2RuO4 and Sr2Rho4 were grown by the author in an effort to study changes of their resistivity with varying temperature and frequency at low temperatures. The crystals were characterized using a variety of x-ray and other techniques, so as to measure their purity. Past work on these materials is discussed and analyzed. Preliminary measurements of the resistivity are presented.

An optical surface roughness model is presented, which allows a reliable determination of the dielectric function of thin films with high surface roughnesses of more than 10 nm peak to valley distance by means of spectroscopic ellipsometry. Starting from histogram evaluation of atomic force microscopy (AFM) topography measurements a specific roughness layer (RL) model was developed for an organic thin film grown in vacuum which is well suited as an example. Theoretical description based on counting statistics allows generalizing the RL model developed to be used for all non-conducting materials. Finally, a direct input of root mean square (RMS) values found by AFM measurements into the proposed model is presented, which is important for complex ellipsometric evaluation models where a reduction of the amount of unknown parameters can be crucial. Exemplarily, the evaluation of a N,N’-dimethoxyethyl-3,4,9,10-perylene-tetracarboxylic-diimide (DiMethoxyethyl-PTCDI) film is presented, which exhibits a very high surface roughness, i.e. showing no homogeneous film at all.

1-Microevaporation - Microfluidics is the branch of fluid mechanics dedicated to the study of flows in the channel withdimensions between 1 micron and 100 micron. The object of this chapter is to illustrate the basicprinciples and possible applications of microfluidic chip, called microevaporator. In the first part ofthe chapter, we present a detailed description of the physics of microevaporators using analyticalarguments, and describe some applications. In the second part of the chapter, we present theexperimental protocol of engineering of micro evaporator and different type of microfluidics device.2- On-chip microspectroscopy - The object of this chapter is to illustrate a method to measure absorption spectra during theprocess of growth of our materials in our microfluidic tools. The aim is to make an opticalcharacterization of our micro materials and to carry-out a spatio-temporal study of kineticproperties of our dispersion under study. This instrumental chapter presents the theoretical basis !of the method we used.3-Role of colloidal stability in the growth of micromaterials - We used combined microspectroscopy and videomicroscopy to follow the nucleation and growth ofmaterials made of core-shell Ag@SiO2 NPs in micro evaporators.!We evidence that the growth is actually not always possible, and instead precipitation may occurduring the concentration process. This event is governed by the concentration of dispersion in thereservoir and we assume that its origin come from ionic species that are concentrated all togetherwith the NPs and may alter the colloidal stability en route towards high concentration. 4-Microfluidic-induced growth and shape-up of three-dimensional extended arrays of denselypacked nano particles - In this chapter I present in details microfluidic evaporation experiments to engineer various denselypacked 3D arrays of NPs.5-Bulk metamaterials assembled by microfluidic evaporation - In this chapter I introduced the technique we used (microspot ellipsometry) in close collaborationswith V.Kravets and A.Grigorenko(University of Manchester) and with A.Aradian, P.Barois, A.Baron,K.Ehrhardt(CRPP, Pessac) to characterized the solids made of densely packed NPs. I describe theconstraints that emerge from the coupling between the small size of our materials and the opticalrequirements, the analysis and interpretation of the ellipsometry experiments show that for thematerial with high volume fraction of metal exists the strong electrical coupling between the NPsand the materials display an extremely high refraction index in the near infra-red regime.

Im Rahmen dieser Arbeit wurden für die Herstellung neuartiger funktioneller Oberflächenbeschichtungen Polymerbürstensysteme basierend auf linearen, thermoresponsiven Poly-2-oxazolinen (POX) entwickelt und ausführlich charakterisiert. Als Grundbaustein für die Herstellung von POX-Bürsten wurden drei endfunktionalisierte thermoresponsive POX mittels kationisch ringöffnender Polymerisation synthetisiert, wobei jeweils 2-Cyclopropyl-2-oxazolin (cPrOX) als thermoresponsive Wiederholungseinheit und 2-Methyl-2-oxazolin (MeOX) als hydrophiles Comonomer zu verschiedenen Anteilen verwendet wurden. Mittels VIS-spektroskopischen Trübungsmessungen wurde für alle POX in Wasser ein LCST-Entmischungsverhalten mit einem reversiblen und scharfen Phasenübergang nachgewiesen, wobei die Trübungstemperaturen stark von der Polymerhydrophilie sowie der Molmasse und der Polymerkonzentration in Lösung abhingen. Die Herstellung der POX-Polymerbürsten auf der Basis der synthetisierten POX erfolgte über einen „grafting to“-Ansatz, bei welchem die Polymere in einem thermisch initiierten Prozess über ein funktionalisiertes Kettenende kovalent an ein Substrat angebunden wurden. Als Hauptmethode zur Charakterisierung der physikochemischen Eigenschaften der hergestellten Schichten, insbesondere deren temperaturabhängiges Schaltverhalten in Wasser, wurde spektroskopische Ellipsometrie verwendet. Zusätzlich kamen Rasterkraftmikroskopie, Kontaktwinkel und Quarzkristallmikrowaage mit Dissipationsaufzeichnung zum Einsatz. Im Gegensatz zum sehr scharfen, diskontinuierlichen Phasenübergang der POX in Lösung konnte für alle POX-Bürsten ein kontinuierlicher Übergang von einem gestreckten Bürstenzustand bei niedrigen Temperaturen in einen kollabierten Zustand bei hohen Temperaturen bestimmt werden, wobei das Quellvermögen und die temperaturabhängigen Quellkurvenverläufe durch die Polymereigenschaften und die Bürstenparameter beeinflussbar waren. Durch die Kombination eines POX mit Polyacrylsäure (PAA) als zweite Komponente konnten zudem neuartige binäre Polymerbürstensysteme hergestellt werden, welche ein komplexes pH- und temperaturabhängiges Schaltverhalten sowie ein steuerbares Proteinadsorptionsvermögen in Abhängigkeit von der Bürstenpräparationsmethodik, der POX-PAA-Zusammensetzung sowie der Temperatur und dem pH-Wert der umgebenden Pufferlösung aufwiesen. Zur ausführlichen Charakterisierung der Schichteigenschaften wurde neben den bereits benannten Methoden der spektroskopischen Ellipsometrie, Rasterkraftmikroskopie und der Kontaktwinkelmessung auch Röntgenphotoelektronenspektroskopie genutzt. Abschließende Zelladhäsionsexperimente mit humanen mesenchymalen Stammzellen auf den bürstenmodifizierte Oberflächen unter physiologischen Bedingungen offenbarten deutliche Unterschiede in der Affinität der Zellen zur Adhäsion auf POX-Homopolymerbürsten in Abhängigkeit der Bürstenhydrophilie. Darüber hinaus konnte die Zelladhäsion auch auf POX-PAA-Mischbürstensystemen gesteuert werden.