The dynamics of ultra-thin polymer films in different confinements studied by resonance enhanced dynamic light scattering

Die Kontroverse über den Glasübergang im Nanometerbereich, z. B. die Glas¬über¬gangs-temperatur Tg von dünnen Polymerfilmen, ist nicht vollständig abgeschlossen. Das dynamische Verhalten auf der Nanoskala ist stark von den einschränkenden Bedingungen abhängig, die auf die Probe wirken. Dünne Polymerfilme sind ideale Systeme um die Dynamik von Polymerketten unter der Einwirkung von Randbedingungen zu untersuchen, wie ich sie in dieser Arbeit variiert habe, um Einblick in dieses Problem zu erhalten.rnrnResonanzverstärkte dynamische Lichtstreuung ist eine Methode, frei von z.B. Fluoreszenzmarkern, die genutzt werden kann um in dünnen Polymerfilmen dynamische Phänomene

Dispersion approach to real and virtual Compton scattering

In recent years, new precision experiments have become possible withthe high luminosity accelerator facilities at MAMIand JLab, supplyingphysicists with precision data sets for different hadronic reactions inthe intermediate energy region, such as pion photo- andelectroproduction and real and virtual Compton scattering.By means of the low energy theorem (LET), the global properties of thenucleon (its mass, charge, and magnetic moment) can be separated fromthe effects of the internal structure of the nucleon, which areeffectively described by polarizabilities. Thepolarizabilities quantify the deformation of the charge andmagnetization densities inside the nucleon in an applied quasistaticelectromagnetic field. The present work is dedicated to develop atool for theextraction of the polarizabilities from these precise Compton data withminimum model dependence, making use of the detailed knowledge of pionphotoproduction by means of dispersion relations (DR). Due to thepresence of t-channel poles, the dispersion integrals for two ofthe six Compton amplitudes diverge. Therefore, we have suggested to subtract the s-channel dispersion integrals at zero photon energy($nu=0$). The subtraction functions at $nu=0$ are calculated through DRin the momentum transfer t at fixed $nu=0$, subtracted at t=0. For this calculation, we use the information about the t-channel process, $gammagammatopipito Nbar{N}$. In this way, four of thepolarizabilities can be predicted using the unsubtracted DR in the $s$-channel. The other two, $alpha-beta$ and $gamma_pi$, are free parameters in ourformalism and can be obtained from a fit to the Compton data.We present the results for unpolarized and polarized RCS observables,%in the kinematics of the most recent experiments, and indicate anenhanced sensitivity to the nucleon polarizabilities in theenergy range between pion production threshold and the $Delta(1232)$-resonance.newlineindentFurthermore,we extend the DR formalism to virtual Compton scattering (radiativeelectron scattering off the nucleon), in which the concept of thepolarizabilities is generalized to the case of avirtual initial photon by introducing six generalizedpolarizabilities (GPs). Our formalism provides predictions for the fourspin GPs, while the two scalar GPs $alpha(Q^2)$ and $beta(Q^2)$ have to befitted to the experimental data at each value of $Q^2$.We show that at energies betweenpion threshold and the $Delta(1232)$-resonance position, thesensitivity to the GPs can be increased significantly, as compared tolow energies, where the LEX is applicable. Our DR formalism can be used for analysing VCS experiments over a widerange of energy and virtuality $Q^2$, which allows one to extract theGPs from VCS data in different kinematics with a minimum of model dependence.

High frequency acoustics in colloid-based meso- and nanostructures by spontaneous Brillouin light scattering

Materials that can mold the flow of elastic waves of certain energy in certain directions are called phononic materials. The present thesis deals essentially with such phononic systems, which are structured in the mesoscale (<1 µm), and with their individual components. Such systems show interesting phononic properties in the hypersonic region, i.e., at frequencies in the GHz range. It is shown that colloidal systems are excellent model systems for the realization of such phononic materials. Therefore, different structures and particle architectures are investigated by Brillouin light scattering, the inelastic scattering of light by phonons.rnThe experimental part of this work is divided into three chapters: Chapter 4 is concerned with the localized mechanical waves in the individual spherical colloidal particles, i.e., with their resonance- or eigenvibrations. The investigation of these vibrations with regard to the environment of the particles, their chemical composition, and the influence of temperature on nanoscopically structured colloids allows novel insights into the physical properties of colloids at small length scales. Furthermore, some general questions concerning light scattering on such systems, in dispute so far, are convincingly addressed.rnChapter 5 is a study of the traveling of mechanical waves in colloidal systems, consisting of ordered and disordered colloids in liquid or elastic matrix. Such systems show acoustic band gaps, which can be explained geometrically (Bragg gap) or by the interaction of the acoustic band with the eigenvibrations of the individual spheres (hybridization gap).rnWhile the latter has no analogue in photonics, the presence of strong phonon scatterers, when a large elastic mismatch between the composite components exists, can largely impact phonon propagation in analogy to strong multiple light scattering systems. The former is exemplified in silica based phononic structures that opens the door to new ways of sound propagation manipulation.rnChapter 6 describes the first measurement of the elastic moduli in newly fabricated by physical vapor deposition so-called ‘stable organic glasses’. rnIn brief, this thesis explores novel phenomena in colloid-based hypersonic phononic structures, utilizing a versatile microfabrication technique along with different colloid architectures provided by material science, and applying a non-destructive optical experimental tool to record dispersion diagrams.rn

Plasmon-enhanced dynamic light scattering of gold nanorods in bulk and near a wall

Transportprozesse von anisotropen metallischen Nanopartikeln wie zum Beispiel Gold-Nanostäbchen in komplexen Flüssigkeiten und/oder begrenzten Geometrien spielen eine bedeutende Rolle in einer Vielzahl von biomedizinischen und industriellen Anwendungen. Ein Weg zu einem tiefen, grundlegenden Verständnis von Transportmechanismen ist die Verwendung zweier leistungsstarker Methoden - dynamischer Lichtstreuung (DLS) und resonanzverstärkter Lichtstreuung (REDLS) in der Nähe einer Grenzfläche. In dieser Arbeit wurden nanomolare Suspensionen von Gold-Nanostäbchen, stabilisiert mit Cetyltrimethylammoniumbromid (CTAB), mit DLS sowie in der Nähe einer Grenzfläche mit REDLS untersucht. Mit DLS wurde eine wellenlängenabhängige Verstärkung der anisotropen Streuung beobachtet, welche sich durch die Anregung von longitudinaler Oberflächenplasmonenresonanz ergibt. Die hohe Streuintensität nahe der longitudinalen Oberflächenplasmonenresonanzfrequenz für Stäbchen, welche parallel zum anregenden optischen Feld liegen, erlaubte die Auflösung der translationalen Anisotropie in einem isotropen Medium. Diese wellenlängenabhängige anisotrope Lichtstreuung ermöglicht neue Anwendungen wie etwa die Untersuchung der Dynamik einzelner Partikel in komplexen Umgebungen mittels depolarisierter dynamischer Lichtstreuung. In der Nähe einer Grenzfläche wurde eine starke Verlangsamung der translationalen Diffusion beobachtet. Hingegen zeigte sich für die Rotation zwar eine ausgeprägte aber weniger starke Verlangsamung. Um den möglichen Einfluss von Ladung auf der festen Grenzfläche zu untersuchen, wurde das Metall mit elektrisch neutralem Polymethylmethacrylat (PMMA) beschichtet. In einem weiteren Ansatz wurde das CTAB in der Gold-Nanostäbchen Lösung durch das kovalent gebundene 16-Mercaptohexadecyltrimethylammoniumbromid (MTAB) ersetzt. Daraus ergab sich eine deutlich geringere Verlangsamung.