Dynamics of settling charged particles in turbulence : theory and experiments

It has been proposed that inertial clustering may lead to an increased collision rate of water droplets in clouds. Atmospheric clouds and electrosprays contain electrically charged particles embedded in turbulent flows, often under the influence of an externally imposed, approximately uniform gravitational or electric force. In this thesis, we present the investigation of charged inertial particles embedded in turbulence. We have developed a theoretical description for the dynamics of such systems of charged, sedimenting particles in turbulence, allowing radial distribution functions to be predicted for both monodisperse and bidisperse particle size distributions. The governing parameters are the particle Stokes number (particle inertial time scale relative to turbulence dissipation time scale), the Coulomb-turbulence parameter (ratio of Coulomb ’terminalar speed to turbulence dissipation velocity scale), and the settling parameter (the ratio of the gravitational terminal speed to turbulence dissipation velocity scale). For the monodispersion particles, The peak in the radial distribution function is well predicted by the balance between the particle terminal velocity under Coulomb repulsion and a time-averaged ’drift’ velocity obtained from the nonuniform sampling of fluid strain and rotation due to finite particle inertia. The theory is compared to measured radial distribution functions for water particles in homogeneous, isotropic air turbulence. The radial distribution functions are obtained from particle positions measured in three dimensions using digital holography. The measurements support the general theoretical expression, consisting of a power law increase in particle clustering due to particle response to dissipative turbulent eddies, modulated by an exponential electrostatic interaction term. Both terms are modified as a result of the gravitational diffusion-like term, and the role of ’gravity’ is explored by imposing a macroscopic uniform electric field to create an enhanced, effective gravity. The relation between the radial distribution functions and inward mean radial relative velocity is established for charged particles.

THE HOLOGRAPHIC DETECTOR FOR CLOUDS FROM TRL 5 TO TRL 8

Clouds are one of the most influential elements of weather on the earth system, yet they are also one of the least understood. Understanding their composition and behavior at small scales is critical to understanding and predicting larger scale feedbacks. Currently, the best method to study clouds on the microscale is through airborne in situ measurements using optical instruments capable of resolving clouds on the individual particle level. However, current instruments are unable to sufficiently resolve the scales important to cloud evolution and behavior. The Holodec is a new generation of optical cloud instrument which uses digital inline holography to overcome many of the limitations of conventional instruments. However, its performance and reliability was limited due to several deficiencies in its original design. These deficiencies were addressed and corrected to advance the instrument from the prototype stage to an operational instrument. In addition, the processing software used to reconstruct and analyze digitally recorded holograms was improved upon to increase robustness and ease of use.

Covalent immobilisation of VEGF on plasma-coated electrospun scaffolds for tissue engineering applications.

Recent findings in the field of biomaterials and tissue engineering provide evidence that surface immobilised growth factors display enhanced stability and induce prolonged function. Cell response can be regulated by material properties and at the site of interest. To this end, we developed scaffolds with covalently bound vascular endothelial growth factor (VEGF) and evaluated their mitogenic effect on endothelial cells in vitro. Nano- (254±133 nm) or micro-fibrous (4.0±0.4 μm) poly(ɛ-caprolactone) (PCL) non-wovens were produced by electrospinning and coated in a radio frequency (RF) plasma process to induce an oxygen functional hydrocarbon layer. Implemented carboxylic acid groups were converted into amine-reactive esters and covalently coupled to VEGF by forming stable amide bonds (standard EDC/NHS chemistry). Substrates were analysed by X-ray photoelectron spectroscopy (XPS), enzyme-linked immuno-assays (ELISA) and immunohistochemistry (anti-VEGF antibody and VEGF-R2 binding). Depending on the reaction conditions, immobilised VEGF was present at 127±47 ng to 941±199 ng per substrate (6mm diameter; concentrations of 4.5 ng mm(-2) or 33.3 ng mm(-2), respectively). Immunohistochemistry provided evidence for biological integrity of immobilised VEGF. Endothelial cell number of primary endothelial cells or immortalised endothelial cells were significantly enhanced on VEGF-functionalised scaffolds compared to native PCL scaffolds. This indicates a sustained activity of immobilised VEGF over a culture period of nine days. We present a versatile method for the fabrication of growth factor-loaded scaffolds at specific concentrations.

Quantitative depth profiling of Ce 3+ in Pt/CeO 2 by in situ high-energy XPS in a hydrogen atmosphere

The redox property of ceria is a key factor in the catalytic activity of ceria-based catalysts. The oxidation state of well-defined ceria nanocubes in gas environments was analysed in situ by a novel combination of near-ambient pressure X-ray Photoelectron Spectroscopy (XPS) and high-energy XPS at a synchrotron X-ray source. In situ high-energy XPS is a promising new tool to determine the electronic structure of matter under defined conditions. The aim was to quantitatively determine the degree of cerium reduction in a nano-structured ceria-supported platinum catalyst as a function of the gas environment. To obtain a non-destructive depth profile at near-ambient pressure, in situ high-energy XPS analysis was performed by varying the kinetic energy of photoelectrons from 1 to 5 keV, and, thus, the probing depth. In ceria nanocubes doped with platinum, oxygen vacancies formed only in the uppermost layers of ceria in an atmosphere of 1 mbar hydrogen and 403 K. For pristine ceria nanocubes, no change in the cerium oxidation state in various hydrogen or oxygen atmospheres was observed as a function of probing depth. In the absence of platinum, hydrogen does not dissociate and, thus, does not lead to reduction of ceria.

Layer-by-layer grown scalable redox-active ruthenium-based molecular multilayer thin films for electrochemical applications and beyond

Here we report the first study on the electrochemical energy storage application of a surface-immobilized ruthenium complex multilayer thin film with anion storage capability. We employed a novel dinuclear ruthenium complex with tetrapodal anchoring groups to build well-ordered redox-active multilayer coatings on an indium tin oxide (ITO) surface using a layer-by-layer self-assembly process. Cyclic voltammetry (CV), UV-Visible (UV-Vis) and Raman spectroscopy showed a linear increase of peak current, absorbance and Raman intensities, respectively with the number of layers. These results indicate the formation of well-ordered multilayers of the ruthenium complex on ITO, which is further supported by the X-ray photoelectron spectroscopy analysis. The thickness of the layers can be controlled with nanometer precision. In particular, the thickest layer studied (65 molecular layers and approx. 120 nm thick) demonstrated fast electrochemical oxidation/reduction, indicating a very low attenuation of the charge transfer within the multilayer. In situ-UV-Vis and resonance Raman spectroscopy results demonstrated the reversible electrochromic/redox behavior of the ruthenium complex multilayered films on ITO with respect to the electrode potential, which is an ideal prerequisite for e.g. smart electrochemical energy storage applications. Galvanostatic charge–discharge experiments demonstrated a pseudocapacitor behavior of the multilayer film with a good specific capacitance of 92.2 F g−1 at a current density of 10 μA cm−2 and an excellent cycling stability. As demonstrated in our prototypical experiments, the fine control of physicochemical properties at nanometer scale, relatively good stability of layers under ambient conditions makes the multilayer coatings of this type an excellent material for e.g. electrochemical energy storage, as interlayers in inverted bulk heterojunction solar cell applications and as functional components in molecular electronics applications.

Nitrogen-Doping in ZnO via Combustion Synthesis?

We report the synthesis and characterization of colored ZnO-based powders via solution combustion reaction of urea and zinc nitrate hexahydrate in varying molar ratios between 1:1 and 10:1. Among other techniques, we employ X-ray diffraction, nuclear magnetic resonance, and Raman spectroscopy to characterize the products. Within a narrow range of reactant ratios, we reproducibly find an unidentified, crystalline precursor phase related to isocyanuric acid next to ZnO. Finally, we complement our investigations by performing Prompt Gamma Activation Analysis (PGAA) on selected products in order to directly determine elemental bulk compositions and compare these with X-ray photoelectron spectroscopy (XPS) measurements. Our data show traces of nitrogen mainly on the surface of the particles, and thus we question the solution combustion method as a reliable synthesis toward N-doped ZnO. Furthermore, we exclude nitrogen as being responsible for the appearance of the four controversially discussed Raman bands superimposed onto the spectrum of pure ZnO (at 275, 510, 582, and 643 cm–1) and show that the combination of PGAA and XPS is an excellent and complementary method to obtain information about the distribution of the elements in question.

Polaronic metal state at the LaAlO₃/SrTiO₃ interface

Interplay of spin, charge, orbital and lattice degrees of freedom in oxide heterostructures results in a plethora of fascinating properties, which can be exploited in new generations of electronic devices with enhanced functionalities. The paradigm example is the interface between the two band insulators LaAlO3 and SrTiO3 that hosts a two-dimensional electron system. Apart from the mobile charge carriers, this system exhibits a range of intriguing properties such as field effect, superconductivity and ferromagnetism, whose fundamental origins are still debated. Here we use soft-X-ray angle-resolved photoelectron spectroscopy to penetrate through the LaAlO3 overlayer and access charge carriers at the buried interface. The experimental spectral function directly identifies the interface charge carriers as large polarons, emerging from coupling of charge and lattice degrees of freedom, and involving two phonons of different energy and thermal activity. This phenomenon fundamentally limits the carrier mobility and explains its puzzling drop at high temperatures.

Si(100) versus Ge(100): Watching the interface formation for the growth of III-V-based solar cells on abundant substrates

We investigated the atomic surface properties of differently prepared silicon and germanium (100) surfaces during metal-organic vapour phase epitaxy/chemical vapour deposition (MOVPE/MOCVD), in particular the impact of the MOVPE ambient, and applied reflectance anisotropy/difference spectroscopy (RAS/RDS) in our MOVPE reactor to in-situ watch and control the preparation on the atomic length scale for subsequent III-V-nucleation. The technological interest in the predominant opto-electronic properties of III-V-compounds drives the research for their heteroepitaxial integration on more abundant and cheaper standard substrates such as Si(100) or Ge(100). In these cases, a general task must be accomplished successfully, i.e. the growth of polar materials on non-polar substrates and, beyond that, very specific variations such as the individual interface formation and the atomic step structure, have to be controlled. Above all, the method of choice to grow industrial relevant high-performance device structures is MOVPE, not normally compatible with surface and interface sensitive characterization tools, which are commonly based on ultrahigh vacuum (UHV) ambients. A dedicated sample transfer system from MOVPE environment to UHV enabled us to benchmark the optical in-situ spectra with results from various surfaces science instruments without considering disruptive contaminants. X-ray photoelectron spectroscopy (XPS) provided direct observation of different terminations such as arsenic and phosphorous and verified oxide removal under various specific process parameters. Absorption lines in Fourier-transform infrared (FTIR) spectra were used to identify specific stretch modes of coupled hydrides and the polarization dependence of the anti-symmetric stretch modes distinguished different dimer orientations. Scanning tunnelling microscopy (STM) studied the atomic arrangement of dimers and steps and tip-induced H-desorption proved the saturation of dangling bonds after preparati- n. In-situ RAS was employed to display details transiently such as the presence of H on the surface at lower temperatures (T <; 800°C) and the absence of Si-H bonds at elevated annealing temperature and also surface terminations. Ge buffer growth by the use of GeH4 enables the preparation of smooth surfaces and leads to a more pronounced amplitude of the features in the spectra which indicates improvements of the surface quality.

XPS as Characterization Tool for PV: From the Substrate to Complete III-V Multijunction Solar Cells

This contribution aims to illustrate the potential of the X-ray photoelectron spectroscopy (XPS) technique as a tool to analyze different parts of a solar cell (surface state, heterointerfaces, profile composition of ohmic contacts, etc). Here, the analysis is specifically applied to III-V multijunction solar cells used in concentrator systems. The information provided from such XPS analysis has helped to understand the physico-chemical nature of these surfaces and interfaces, and thus has guided the technological process in order to improve the solar cell performance.

Radio-holografía de microondas para la optimización de la superficie de grandes antenas reflectoras

En el presente trabajo de tesis se afronta el problema de la optimización de la superficie de grandes antenas reflectoras. Es sabido que los grandes reflectores, formados por una superficie panelada, sufren deformaciones debidas al impacto del viento, a los cambios de temperatura y a los efectos gravitacionales derivados del gran peso de la estructura. Estos efectos hacen que los reflectores pierdan su forma ideal, generalmente de paraboloide, y se reduzca su eficiencia de apertura y, por tanto, se limite la máxima frecuencia de uso de los mismos. Es necesario, por tanto, disponer de técnicas que permitan medir el estado de la superficie de grandes reflectores, y derivar los ajustes necesarios a aplicar sobre los tornillos de soporte de cada uno de los paneles que conforman dicha superficie. De esta manera, se devolvería al reflector su forma óptima y aumentaría la eficiencia de apertura y el rango de frecuencias de uso. Hay que resaltar que el aumento de la eficiencia de un radiotelescopio supone una reducción en el tiempo de integración necesario para la detección de las debilísimas señales generadas por las radiofuentes naturales, ahorrando así valioso tiempo de observación. Además, el incremento en el rango de frecuencias permite la detección de nuevas líneas o especies moleculares en dichas radiofuentes. Tras un primer capítulo introductorio, se presenta, en el capítulo segundo, la geometría de estos grandes reflectores y la influencia de los distintos factores que afectan a la calidad de la superficie de los mismos, como la gravedad, el viento y la temperatura, particularizando para el caso del radiotelescopio de 40 metros del Centro Astronómico de Yebes. En el tercer capítulo, se presentan las diferentes técnicas metrológicas empleadas actualmente para abordar la determinación de estos ajustes, mostrándose las ventajas e inconvenientes de cada una de ellas. Actualmente, la técnica metrológica más precisa y rápida para llevar a cabo esta tarea de caracterización de la superficie de un gran reflector, es la radio-holografía de microondas presentada en el capítulo cuarto. A partir de las medidas proporcionadas por esta técnica, realizadas con la ayuda de un transmisor, y mediante transformaciones de campo, se calculan los errores de la superficie del reflector, respecto al paraboloide ideal, y se derivan los ajustes necesarios. En los capítulos quinto y sexto se presentan los resultados de la aplicación de esta técnica a dos radiotelescopios: el de 30 metros de IRAM en Pico de Veleta (Granada) y los prototipos de 12 metros de las antenas del proyecto ALMA. Por su parte, el capítulo séptimo contiene el núcleo fundamental de esta tesis y presenta el desarrollo de la técnica de radio-holografía de microondas para optimizar la superficie del radiotelescopio de 40 metros del Centro Astronómico de Yebes. Para ello, ha sido necesario diseñar, construir e instalar un receptor de doble canal en banda Ku en foco primario, y la instrumentación asociada para hacer las medidas de amplitud y fase del diagrama de radiación. Además, ha sido necesario desarrollar el software para llevar a cabo las transformaciones de campo y derivar los ajustes de los paneles. De las medidas holográficas iniciales resultó un error de la superficie del radiotelescopio de 485 μm WRMS, respecto al paraboloide ideal en dirección normal. Tras varias iteraciones del proceso de medida y ajuste, se consiguió reducir dicho error a 194 μm WRMS. Esta notable mejora de la calidad de la superficie ha supuesto aumentar la eficiencia de apertura desde 2,6% al 38,2% a 86 GHz, para un receptor a esta frecuencia situado en el foco primario que produjese la misma iluminación que el receptor de holografía. In this thesis the problem of large reflector antenna surface optimization is faced. It is well known that large reflectors, which are made of a panelled surface, suffer from deformations due to the impact of wind, temperature gradients and gravity loads coming from the high weigth of the structure. These effects distort the ideal reflector shape, which is a paraboloid in most cases, hence reducing the aperture efficiency of the reflector and limiting the maximum frequency of operation. Therefore, it is necessary to have some techniques to measure the status of large reflector surfaces and to derive the adjustment values to be applied to the screws that connect the surface panels to the reflector back-up structure. In this way, the reflector would recover its optimum shape and the aperture efficiency and frequency range would increase. It has to be stated that an increment in the radiotelescope aperture efficiency would imply a reduction in the integration time needed to detect such weak signals coming from natural radiosources in space and, hence, an important saving in observation time. In addition, the increase in the frequency range of operation would allow the detection of new molecular lines in those radiosources. After the introduction, the second chapter shows the geometry of large reflector antennas and the impact on its surface quality of different factors like gravity, wind and temperature, particularly for the case of the Centro Astronómico de Yebes 40 meter radiotelescope. The third chapter deals with the different metrology techniques used to determine the panel adjustments, including the advantages and drawbacks of each one Currently, the most accurate and fast metrologic technique to carry out the characterization of large reflector surfaces is microwave radio-holography2, which is shown in chapter four. From the measurements provided by microwave radio-holography, performed with the help of a transmitter, and with the use of field transformations, the reflector surface errors are computed and the panel adjustments are derived. Chapters five and six show the results of holographic measurements applied to two first class radiotelescopes: the IRAM 30 meter radiotelescope and the 12 meter prototype antennas for the ALMA project. Chapter seven contains the main work of this thesis. It presents the development of the microwave radio-holography technique for the optimization of the Centro Astronómico de Yebes 40m radiotelescope. The work implied the design, construction and instalation of a prime focus Ku-band dual channel receiver, together with the associated instrumentation to measure the amplitude and phase of the radiotelescope radiation pattern. In addition, the software to carry out field transformations and screw settings computations was developed too. Initial holography measurements came up with an surface error of 485 μmWRMS in normal direction with respect to the best-fit paraboloid. After a few iterations of the measurementadjustment cycle, the surface error was reduced to 194 μm WRMS. This remarkable improvement in surface quality means an increment in aperture efficiency from 2,6% to 38,2% at 86 GHz, assuming a receiver at this frequency in prime focus position which produces the same illumination as the holography receiver.

Valence photoionization of the N2 molecule in the region of the N 1s→Rydberg excitations

The intensities of the X and A valence photoelectron lines of N2 have been found to display Fano line shapes as a function of photon energy around the N 1s→ Rydberg excitations. The vibrational intensity distributions of these photoelectron lines change at the N 1s→3sσ and 3pπ resonances. These effects indicate interference between direct and resonant photoionization channels. Our numerical simulations reproduce quite well the experimental results.

Self-assembled MgxZn1−xO quantum dots (0 ≤ x ≤ 1) on different substrates using spray pyrolysis methodology

By using the spray pyrolysis methodology in its classical configuration we have grown self-assembled MgxZn1−xO quantum dots (size [similar]4–6 nm) in the overall range of compositions 0 ≤ x ≤ 1 on c-sapphire, Si (100) and quartz substrates. Composition of the quantum dots was determined by means of transmission electron microscopy-energy dispersive X-ray analysis (TEM-EDAX) and X-ray photoelectron spectroscopy. Selected area electron diffraction reveals the growth of single phase hexagonal MgxZn1−xO quantum dots with composition 0 ≤ x ≤ 0.32 by using a nominal concentration of Mg in the range 0 to 45%. Onset of Mg concentration about 50% (nominal) forces the hexagonal lattice to undergo a phase transition from hexagonal to a cubic structure which resulted in the growth of hexagonal and cubic phases of MgxZn1−xO in the intermediate range of Mg concentrations 50 to 85% (0.39 ≤ x ≤ 0.77), whereas higher nominal concentration of Mg ≥ 90% (0.81 ≤ x ≤ 1) leads to the growth of single phase cubic MgxZn1−xO quantum dots. High resolution transmission electron microscopy and fast Fourier transform confirm the results and show clearly distinguishable hexagonal and cubic crystal structures of the respective quantum dots. A difference of 0.24 eV was detected between the core levels (Zn 2p and Mg 1s) measured in quantum dots with hexagonal and cubic structures by X-ray photoemission. The shift of these core levels can be explained in the frame of the different coordination of cations in the hexagonal and cubic configurations. Finally, the optical absorption measurements performed on single phase hexagonal MgxZn1−xO QDs exhibited a clear shift in optical energy gap on increasing the Mg concentration from 0 to 40%, which is explained as an effect of substitution of Zn2+ by Mg2+ in the ZnO lattice.

In situ study of Ge(100) surfaces with tertiarybutylphosphine supply in vapor phase epitaxy ambient

GaInP nucleation on Ge(100) often starts by annealing of the Ge(100) substrates under supply of phosphorus precursors. However, the influence on the Ge surface is not well understood. Here, we studied vicinal Ge(100) surfaces annealed under tertiarybutylphosphine (TBP) supply in MOVPE by in situ reflection anisotropy spectroscopy (RAS), X-ray photoelectron spectroscopy (XPS), and low energy electron diffraction (LEED). While XPS reveals a P termination and the presence of carbon on the Ge surface, LEED patterns indicate a disordered surface probably due to by-products of the TBP pyrolysis. However, the TBP annealed Ge(100) surface exhibits a characteristic RA spectrum, which is related to the P termination. RAS allows us to in situ control phosphorus desorption dependent on temperature.

In situ control of As dimer orientation on Ge(100) surfaces

We investigated the preparation of single domain Ge(100):As surfaces in a metal-organic vapor phase epitaxy reactor. In situ reflection anisotropy spectra (RAS) of vicinal substrates change when arsenic is supplied either by tertiarybutylarsine or by background As4 during annealing. Low energy electron diffraction shows mutually perpendicular orientations of dimers, scanning tunneling microscopy reveals distinct differences in the step structure, and x-ray photoelectron spectroscopy confirms differences in the As coverage of the Ge(100): As samples. Their RAS signals consist of contributions related to As dimer orientation and to step structure, enabling precise in situ control over preparation of single domain Ge(100): As surfaces.

Single - and double energy swift and slow heavy ion irradiated optical waveguides in Er: Tungstene-Tellurite glass and BGO for telecom applications

The fabrication of broadband amplifiers in wavelength division multiplexing (WDM) around 1.55 m, as they exhibit large stimulated cross sections and broad emission bandwidth. Bi4Ge3O12 (eultine type BGO) - well known scintillator material, also a rare-earth host material, photorefractive waveguides produced in it only using light ions in the past. Recently: MeV N+ ions and swift O5+ and C5+ ions, too*. Bi12GeO20 (sillenite type BGO) - high photoconductivity and photorefractive sensitivity in the visible and NIR good candidate for real-time holography and optical phase conjugation, photorefractive waveguides produced in it only using light ions. No previous attempts of ion beam fabrication of waveguides in it.