Decay of imprinted surface waves in polymers

CONCLUSIONS The focus of this work was the investigation ofanomalies in Tg and dynamics at polymer surfaces. Thethermally induced decay of hot-embossed polymer gratings isstudied using laser-diffraction and atomic force microscopy(AFM). Monodisperse PMMA and PS are selected in the Mwranges of 4.2 to 65.0 kg/mol and 3.47 to 65.0 kg/mol,respectively. Two different modes of measurement were used:the one mode uses temperature ramps to obtain an estimate ofthe near-surface glass temperature, Tdec,0; the other modeinvestigates the dynamics at a constant temperature aboveTg. The temperature-ramp experiments reveal Tdec,0 valuesvery close to the Tg,bulk values, as determined bydifferential scanning calorimetry (DSC). The PMMA of65.0 kg/mol shows a decreased value of Tg, while the PS samples of 3.47 and 10.3 kg/mol (Mw

Quantum effects and dynamics in hydrogen-bonded systems: a first-principles approach to spectroscopic experiments

Computer simulations have become an important tool in physics. Especially systems in the solid state have been investigated extensively with the help of modern computational methods. This thesis focuses on the simulation of hydrogen-bonded systems, using quantum chemical methods combined with molecular dynamics (MD) simulations. MD simulations are carried out for investigating the energetics and structure of a system under conditions that include physical parameters such as temperature and pressure. Ab initio quantum chemical methods have proven to be capable of predicting spectroscopic quantities. The combination of these two features still represents a methodological challenge. Furthermore, conventional MD simulations consider the nuclei as classical particles. Not only motional effects, but also the quantum nature of the nuclei are expected to influence the properties of a molecular system. This work aims at a more realistic description of properties that are accessible via NMR experiments. With the help of the path integral formalism the quantum nature of the nuclei has been incorporated and its influence on the NMR parameters explored. The effect on both the NMR chemical shift and the Nuclear Quadrupole Coupling Constants (NQCC) is presented for intra- and intermolecular hydrogen bonds. The second part of this thesis presents the computation of electric field gradients within the Gaussian and Augmented Plane Waves (GAPW) framework, that allows for all-electron calculations in periodic systems. This recent development improves the accuracy of many calculations compared to the pseudopotential approximation, which treats the core electrons as part of an effective potential. In combination with MD simulations of water, the NMR longitudinal relaxation times for 17O and 2H have been obtained. The results show a considerable agreement with the experiment. Finally, an implementation of the calculation of the stress tensor into the quantum chemical program suite CP2K is presented. This enables MD simulations under constant pressure conditions, which is demonstrated with a series of liquid water simulations, that sheds light on the influence of the exchange-correlation functional used on the density of the simulated liquid.

Numerical coupling of thermal-electric network models and energy-transport equations including optoelectronic semiconductor devices

In this work the numerical coupling of thermal and electric network models with model equations for optoelectronic semiconductor devices is presented. Modified nodal analysis (MNA) is applied to model electric networks. Thermal effects are modeled by an accompanying thermal network. Semiconductor devices are modeled by the energy-transport model, that allows for thermal effects. The energy-transport model is expandend to a model for optoelectronic semiconductor devices. The temperature of the crystal lattice of the semiconductor devices is modeled by the heat flow eqaution. The corresponding heat source term is derived under thermodynamical and phenomenological considerations of energy fluxes. The energy-transport model is coupled directly into the network equations and the heat flow equation for the lattice temperature is coupled directly into the accompanying thermal network. The coupled thermal-electric network-device model results in a system of partial differential-algebraic equations (PDAE). Numerical examples are presented for the coupling of network- and one-dimensional semiconductor equations. Hybridized mixed finite elements are applied for the space discretization of the semiconductor equations. Backward difference formluas are applied for time discretization. Thus, positivity of charge carrier densities and continuity of the current density is guaranteed even for the coupled model.

Detection of small buried objects: asymptotic factorization and MUSIC

In this work, we consider a simple model problem for the electromagnetic exploration of small perfectly conducting objects buried within the lower halfspace of an unbounded two–layered background medium. In possible applications, such as, e.g., humanitarian demining, the two layers would correspond to air and soil. Moving a set of electric devices parallel to the surface of ground to generate a time–harmonic field, the induced field is measured within the same devices. The goal is to retrieve information about buried scatterers from these data. In mathematical terms, we are concerned with the analysis and numerical solution of the inverse scattering problem to reconstruct the number and the positions of a collection of finitely many small perfectly conducting scatterers buried within the lower halfspace of an unbounded two–layered background medium from near field measurements of time–harmonic electromagnetic waves. For this purpose, we first study the corresponding direct scattering problem in detail and derive an asymptotic expansion of the scattered field as the size of the scatterers tends to zero. Then, we use this expansion to justify a noniterative MUSIC–type reconstruction method for the solution of the inverse scattering problem. We propose a numerical implementation of this reconstruction method and provide a series of numerical experiments.

Nanoscopic studies of conjugated polymer blends by (electric) scanning probe microscopy

Conjugated polymers and conjugated polymer blends have attracted great interest due to their potential applications in biosensors and organic electronics. The sub-100 nm morphology of these materials is known to heavily influence their electromechanical properties and the performance of devices they are part of. Electromechanical properties include charge injection, transport, recombination, and trapping, the phase behavior and the mechanical robustness of polymers and blends. Electrical scanning probe microscopy techniques are ideal tools to measure simultaneously electric (conductivity and surface potential) and dielectric (dielectric constant) properties, surface morphology, and mechanical properties of thin films of conjugated polymers and their blends.rnIn this thesis, I first present a combined topography, Kelvin probe force microscopy (KPFM), and scanning conductive torsion mode microscopy (SCTMM) study on a gold/polystyrene model system. This system is a mimic for conjugated polymer blends where conductive domains (gold nanoparticles) are embedded in a non-conductive matrix (polystyrene film), like for polypyrrole:polystyrene sulfonate (PPy:PSS), and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). I controlled the nanoscale morphology of the model by varying the distribution of gold nanoparticles in the polystyrene films. I studied the influence of different morphologies on the surface potential measured by KPFM and on the conductivity measured by SCTMM. By the knowledge I gained from analyzing the data of the model system I was able to predict the nanostructure of a homemade PPy:PSS blend.rnThe morphologic, electric, and dielectric properties of water based conjugated polymer blends, e.g. PPy:PSS or PEDOT:PSS, are known to be influenced by their water content. These properties also influence the macroscopic performance when the polymer blends are employed in a device. In the second part I therefore present an in situ humidity-dependence study on PPy:PSS films spin-coated and drop-coated on hydrophobic highly ordered pyrolytic graphite substrates by KPFM. I additionally used a particular KPFM mode that detects the second harmonic electrostatic force. With this, I obtained images of dielectric constants of samples. Upon increasing relative humidity, the surface morphology and composition of the films changed. I also observed that relative humidity affected thermally unannealed and annealed PPy:PSS films differently. rnThe conductivity of a conjugated polymer may change once it is embedded in a non-conductive matrix, like for PPy embedded in PSS. To measure the conductivity of single conjugated polymer particles, in the third part, I present a direct method based on microscopic four-point probes. I started with metal core-shell and metal bulk particles as models, and measured their conductivities. The study could be extended to measure conductivity of single PPy particles (core-shell and bulk) with a diameter of a few micrometers.

Measurement of the elastic electron-proton cross section and separation of the electric and magnetic form factor in the Q 2 range from 0.004 to 1 (GeV/c) 2

The electromagnetic form factors of the proton are fundamental quantities sensitive to the distribution of charge and magnetization inside the proton. Precise knowledge of the form factors, in particular of the charge and magnetization radii provide strong tests for theory in the non-perturbative regime of QCD. However, the existing data at Q^2 below 1 (GeV/c)^2 are not precise enough for a hard test of theoretical predictions.rnrnFor a more precise determination of the form factors, within this work more than 1400 cross sections of the reaction H(e,e′)p were measured at the Mainz Microtron MAMI using the 3-spectrometer-facility of the A1-collaboration. The data were taken in three periods in the years 2006 and 2007 using beam energies of 180, 315, 450, 585, 720 and 855 MeV. They cover the Q^2 region from 0.004 to 1 (GeV/c)^2 with counting rate uncertainties below 0.2% for most of the data points. The relative luminosity of the measurements was determined using one of the spectrometers as a luminosity monitor. The overlapping acceptances of the measurements maximize the internal redundancy of the data and allow, together with several additions to the standard experimental setup, for tight control of systematic uncertainties.rnTo account for the radiative processes, an event generator was developed and implemented in the simulation package of the analysis software which works without peaking approximation by explicitly calculating the Bethe-Heitler and Born Feynman diagrams for each event.rnTo separate the form factors and to determine the radii, the data were analyzed by fitting a wide selection of form factor models directly to the measured cross sections. These fits also determined the absolute normalization of the different data subsets. The validity of this method was tested with extensive simulations. The results were compared to an extraction via the standard Rosenbluth technique.rnrnThe dip structure in G_E that was seen in the analysis of the previous world data shows up in a modified form. When compared to the standard-dipole form factor as a smooth curve, the extracted G_E exhibits a strong change of the slope around 0.1 (GeV/c)^2, and in the magnetic form factor a dip around 0.2 (GeV/c)^2 is found. This may be taken as indications for a pion cloud. For higher Q^2, the fits yield larger values for G_M than previous measurements, in agreement with form factor ratios from recent precise polarized measurements in the Q2 region up to 0.6 (GeV/c)^2.rnrnThe charge and magnetic rms radii are determined as rn⟨r_e⟩=0.879 ± 0.005(stat.) ± 0.004(syst.) ± 0.002(model) ± 0.004(group) fm,rn⟨r_m⟩=0.777 ± 0.013(stat.) ± 0.009(syst.) ± 0.005(model) ± 0.002(group) fm.rnThis charge radius is significantly larger than theoretical predictions and than the radius of the standard dipole. However, it is in agreement with earlier results measured at the Mainz linear accelerator and with determinations from Hydrogen Lamb shift measurements. The extracted magnetic radius is smaller than previous determinations and than the standard-dipole value.

Investigation of the electric field enhanced PNA-DNA hybridization on Au surface by using surface plasmon field-enhanced fluorescence spectroscopy (SPFS)

Recently, the surface plasmon field-enhanced fluorescence spectroscopy (SPFS) was developed as a kinetic analysis and a detection method with dual- monitoring of the change of reflectivity and fluorescence signal for the interfacial phenomenon. A fundamental study of PNA and DNA interaction at the surface using surface plasmon fluorescence spectroscopy (SPFS) will be investigated in studies. Furthermore, several specific conditions to influence on PNA/DNA hybridization and affinity efficiency by monitoring reflective index changes and fluorescence variation at the same time will be considered. In order to identify the affinity degree of PNA/DNA hybridizaiton at the surface, the association constant (kon) and the dissociation constant (koff) will be obtained by titration experiment of various concentration of target DNA and kinetic investigation. In addition, for more enhancing the hybridization efficiency of PNA/DNA, a study of polarized electric field enhancement system will be introduced and performed in detail. DNA is well-known polyelectrolytes with naturally negative charged molecules in its structure. With polarized electrical treatment, applying DC field to the metal surface, which PNA probe would be immobilized at, negatively charged DNA molecules can be attracted by electromagnetic attraction force and manipulated to the close the surface area, and have more possibility to hybridize with probe PNA molecules by hydrogen bonding each corresponding base sequence. There are several major factors can be influenced on the hybridization efficiency.

The search for the neutron electric dipole moment

A permanent electric dipole moment of the neutron violates time reversal as well as parity symmetry. Thus it also violates the combination of charge conjugation and parity symmetry if the combination of all three symmetries is a symmetry of nature. The violation of these symmetries could help to explain the observed baryon content of the Universe. The prediction of the Standard Model of particle physics for the neutron electric dipole moment is only about 10e−32 ecm. At the same time the combined violation of charge conjugation and parity symmetry in the Standard Model is insufficient to explain the observed baryon asymmetry of the Universe. Several extensions to the Standard Model can explain the observed baryon asymmetry and also predict values for the neutron electric dipole moment just below the current best experimental limit of d n < 2.9e−26 ecm, (90% C.L.) that has been obtained by the Sussex-RAL-ILL collaboration in 2006. The very same experiment that set the current best limit on the electric dipole moment has been upgraded and moved to the Paul Scherrer Institute. Now an international collaboration is aiming at increasing the sensitivity for an electric dipole moment by more than an order of magnitude. This thesis took place in the frame of this experiment and went along with the commissioning of the experiment until first data taking. After a short layout of the theoretical background in chapter 1, the experiment with all subsystems and their performance are described in detail in chapter 2. To reach the goal sensitivity the control of systematic errors is as important as an increase in statistical sensitivity. Known systematic efects are described and evaluated in chapter 3. During about ten days in 2012, a first set of data was measured with the experiment at the Paul Scherrer Institute. An analysis of this data is presented in chapter 4, together with general tools developed for future analysis eforts. The result for the upper limit of an electric dipole moment of the neutron is |dn| ≤ 6.4e−25 ecm (95%C.L.). Chapter 5 presents investigations for a next generation experiment, to build electrodes made partly from insulating material. Among other advantages, such electrodes would reduce magnetic noise, generated by the thermal movement of charge carriers. The last Chapter summarizes this work and gives an outlook.

Hypersonic phonon propagation in mesoscopic systems by Brillouin spectroscopy

Phononic crystals, capable to block or direct the propagation of elastic/acoustic waves, have attracted increasing interdisciplinary interest across condensed matter physics and materials science. As of today, no generalized full description of elastic wave propagation in phononic structures is available, mainly due to the large number of variables determining the band diagram. Therefore, this thesis aims for a deeper understanding of the fundamental concepts governing wave propagation in mesoscopic structures by investigation of appropriate model systems. The phononic dispersion relation at hypersonic frequencies is directly investigated by the non-destructive technique of high-resolution spontaneous Brillouin light scattering (BLS) combined with computational methods. Due to the vector nature of the elastic wave propagation, we first studied the hypersonic band structure of hybrid superlattices. These 1D phononic crystals composed of alternating layers of hard and soft materials feature large Bragg gaps. BLS spectra are sensitive probes of the moduli, photo-elastic constants and structural parameters of the constituent components. Engineering of the band structure can be realized by introduction of defects. Here, cavity layers are employed to launch additional modes that modify the dispersion of the undisturbed superlattice, with extraordinary implications to the band gap region. Density of states calculations in conjunction with the associated deformation allow for unambiguous identication of surface and cavity modes, as well as their interaction with adjacent defects. Next, the role of local resonances in phononic systems is explored in 3D structures based on colloidal particles. In turbid media BLS records the particle vibration spectrum comprising resonant modes due to the spatial confinement of elastic energy. Here, the frequency and lineshapes of the particle eigenmodes are discussed as function of increased interaction and departure from spherical symmetry. The latter is realized by uniaxial stretching of polystyrene spheres, that can be aligned in an alternating electric field. The resulting spheroidal crystals clearly exhibit anisotropic phononic properties. Establishing reliable predictions of acoustic wave propagation, necessary to advance, e.g., optomechanics and phononic devices is the ultimate aim of this thesis.