Redox-Switching in a Viologen-type Adlayer: An Electrochemical Shell-Isolated Nanoparticle Enhanced Raman Spectroscopy Study on Au(111)-(1 x 1) Single Crystal Electrodes

We reported the first application of in situ shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS) to an interfacial redox reaction under electrochemical conditions. We construct gap-mode sandwich structures composed of a thiol-terminated HS-6V6H viologen adlayer immobilized on a single crystal Au(111)-(1x1) electrode and covered by Au(60 nm)@SlO(2) core shell nanoparticles acting as plasmonic antennas. We observed high-quality, potential-dependent Raman spectra of the three viologen species V(2+),V(+center dot) and V(0) on a well-defined Au(111) substrate surface and could map their potential-dependent evolution. Comparison with experiments on powder samples revealed an enhancement factor of the nonresonant Raman modes of similar to 3 x 10(5), and up to 9 x 10(7) for the resonance modes. The study illustrates the unique capability of SHINERS and its potential in the entire field of electrochemical surface science to explore structures and reaction pathways on well-defined substrate surfaces, such as single crystals, for molecular, (electro-)- catalytic, bioelectrochemical systems up to fundamental double layer studies at electrified solid/liquid interfaces.

Diffusion-driven transport in clayrock formations

Clay mineral-rich sedimentary formations are currently under investigation to evaluate their potential use as host formations for installation of deep underground disposal facilities for radioactive waste (e.g. Boom Clay (BE), Opalinus Clay (CH), Callovo-Oxfordian argillite (FR)). The ultimate safety of the corresponding repository concepts depends largely on the capacity of the host formation to limit the flux towards the biosphere of radionuclides (RN) contained in the waste to acceptably low levels. Data for diffusion-driven transfer in these formations shows extreme differences in the measured or modelled behaviour for various radionuclides, e. g. between halogen RN (Cl-36, I-129) and actinides (U-238,U-235, Np-237, Th-232, etc.), which result from major differences between RN of the effects on transport of two phenomena: diffusion and sorption. This paper describes recent research aimed at improving understanding of these two phenomena, focusing on the results of studies carried out during the EC Funmig IP on clayrocks from the above three formations and from the Boda formation (HU). Project results regarding phenomena governing water, cation and anion distribution and mobility in the pore volumes influenced by the negatively-charged surfaces of clay minerals show a convergence of the modelling results for behaviour at the molecular scale and descriptions based on electrical double layer models. Transport models exist which couple ion distribution relative to the clay-solution interface and differentiated diffusive characteristics. These codes are able to reproduce the main trends in behaviour observed experimentally, e.g. D-e(anion) < D-e(HTO) < D-e(cation) and D-e(anion) variations as a function of ionic strength and material density. These trends are also well-explained by models of transport through ideal porous matrices made up of a charged surface material. Experimental validation of these models is good as regards monovalent alkaline cations, in progress for divalent electrostatically-interacting cations (e.g. Sr2+) and still relatively poor for 'strongly sorbing', high K-d cations. Funmig results have clarified understanding of how clayrock mineral composition, and the corresponding organisation of mineral grain assemblages and their associated porosity, can affect mobile solute (anions, HTO) diffusion at different scales (mm to geological formation). In particular, advances made in the capacity to map clayrock mineral grain-porosity organisation at high resolution provide additional elements for understanding diffusion anisotropy and for relating diffusion characteristics measured at different scales. On the other hand, the results of studies focusing on evaluating the potential effects of heterogeneity on mobile species diffusion at the formation scale tend to show that there is a minimal effect when compared to a homogeneous property model. Finally, the results of a natural tracer-based study carried out on the Opalinus Clay formation increase confidence in the use of diffusion parameters measured on laboratory scale samples for predicting diffusion over geological time-space scales. Much effort was placed on improving understanding of coupled sorption-diffusion phenomena for sorbing cations in clayrocks. Results regarding sorption equilibrium in dispersed and compacted materials for weakly to moderately sorbing cations (Sr2+, Cs+, Co2+) tend to show that the same sorption model probably holds in both systems. It was not possible to demonstrate this for highly sorbing elements such as Eu(III) because of the extremely long times needed to reach equilibrium conditions, but there does not seem to be any clear reason why such elements should not have similar behaviour. Diffusion experiments carried out with Sr2+, Cs+ and Eu(III) on all of the clayrocks gave mixed results and tend to show that coupled diffusion-sorption migration is much more complex than expected, leading generally to greater mobility than that predicted by coupling a batch-determined K-d and Ficks law based on the diffusion behaviour of HTO. If the K-d measured on equivalent dispersed systems holds as was shown to be the case for Sr, Cs (and probably Co) for Opalinus Clay, these results indicate that these cations have a D-e value higher than HTO (up to a factor of 10 for Cs+). Results are as yet very limited for very moderate to strongly sorbing species (e.g. Co(II), Eu(III), Cu(II)) because of their very slow transfer characteristics. (C) 2011 Elsevier Ltd. All rights reserved.

Reconstruction of the palatal aponeurosis with autogenous fascia lata in secondary radical intravelar veloplasty: a new method

Velopharyngeal insufficiency in cleft patients with muscular insufficiency detected by nasendoscopy is commonly treated by secondary radical intravelar veloplasty, in which the palatal muscles are reoriented and positioned backwards. The dead space between the retro-displaced musculature and the posterior borders of the palatal bone remains problematic. Postoperatively, the surgically achieved lengthening of the soft palate often diminishes due to scar tissue formation in the dead space, leading to reattachment of the reoriented muscles to the palatal bone and to decreased mobility of the soft palate. To avoid this, the dead space should be restored by a structure imitating the function of the missing palatal aponeurosis. The entire dead space was covered using a double layer of autogenous fascia lata harvested from the lateral thigh, which should allow sufficient and permanent sliding of the retro-positioned musculature. A clinical case of a 9-year-old boy who underwent the operation is reported. Postoperatively, marked functional improvements were observable in speech assessment, nasendoscopy and nasometry. The case reported here suggests that the restoration of the dead space may be beneficial for effective secondary palatal repair. Fascia lata seems to be a suitable graft for this purpose.

RF-sputter fabrication of magnetic garnet thin films and simulation modeling for 1-D magnetic photonic crystal waveguide devices

One dimensional magnetic photonic crystals (1D-MPC) are promising structures for integrated optical isolator applications. Rare earth substituted garnet thin films with proper Faraday rotation are required to fabricate planar 1D-MPCs. In this thesis, flat-top response 1D-MPC was proposed and spectral responses and Faraday rotation were modeled. Bismuth substituted iron garnet films were fabricated by RF magnetron sputtering and structures, compositions, birefringence and magnetooptical properties were studied. Double layer structures for single mode propagation were also fabricated by sputtering for the first time. Multilayer stacks with multiple defects (phase shift) composed of Ce-YIG and GGG quarter-wave plates were simulated by the transfer matrix method. The transmission and Faraday rotation characteristics were theoretically studied. It is found that flat-top response, with 100% transmission and near 45o rotation is achievable by adjusting the inter-defect spacing, for film structures as thin as 30 to 35 μm. This is better than 3-fold reduction in length compared to the best Ce-YIG films for comparable rotations, thus allows a considerable reduction in size in manufactured optical isolators. Transmission bands as wide as 7nm were predicted, which is considerable improvement over 2 defects structure. Effect of repetition number and ratio factor on transmission and Faraday rotation ripple factors for the case of 3 and 4 defects structure has been discussed. Diffraction across the structure corresponds to a longer optical path length. Thus the use of guided optics is required to minimize the insertion losses in integrated devices. This part is discussed in chapter 2 in this thesis. Bismuth substituted iron garnet thin films were prepared by RF magnetron sputtering. We investigated or measured the deposition parameters optimization, crystallinity, surface morphologies, composition, magnetic and magnetooptical properties. A very high crystalline quality garnet film with smooth surface has been heteroepitaxially grown on (111) GGG substrate for films less than 1μm. Dual layer structures with two distinct XRD peaks (within a single sputtered film) start to develop when films exceed this thickness. The development of dual layer structure was explained by compositional gradient across film thickness, rather than strain gradient proposed by other authors. Lower DC self bias or higher substrate temperature is found to help to delay the appearance of the 2nd layer. The deposited films show in-plane magnetization, which is advantageous for waveguide devices application. Propagation losses of fabricated waveguides can be decreased by annealing in an oxygen atmosphere from 25dB/cm to 10dB/cm. The Faraday rotation at λ=1.55μm were also measured for the waveguides. FR is small (10° for a 3mm long waveguide), due to the presence of linear birefringence. This part is covered in chapter 4. We also investigated the elimination of linear birefringence by thickness tuning method for our sputtered films. We examined the compressively and tensilely strained films and analyze the photoelastic response of the sputter deposited garnet films. It has been found that the net birefringence can be eliminated under planar compressive strain conditions by sputtering. Bi-layer GGG on garnet thin film yields a reduced birefringence. Temperature control during the sputter deposition of GGG cover layer is critical and strongly influences the magnetization and birefringence level in the waveguide. High temperature deposition lowers the magnetization and increases the linear birefringence in the garnet films. Double layer single mode structures fabricated by sputtering were also studied. The double layer, which shows an in-plane magnetization, has an increased RMS roughness upon upper layer deposition. The single mode characteristic was confirmed by prism coupler measurement. This part is discussed in chapter 5.

STUDY OF HYBRID ELECTRIC VEHICLE BATTERY MODELING AND CONTROL USING AUTONOMIE

This report presents the research results of battery modeling and control for hybrid electric vehicles (HEV). The simulation study is conducted using plug-and-play powertrain and vehicle development software, Autonomie. The base vehicle model used for testing the performance of battery model and battery control strategy is the Prius MY04, a power-split hybrid electric vehicle model in Autonomie. To evaluate the battery performance for HEV applications, the Prius MY04 model and its powertrain energy flow in various vehicle operating modes are analyzed. The power outputs of the major powertrain components under different driving cycles are discussed with a focus on battery performance. The simulation results show that the vehicle fuel economy calculated by the Autonomie Prius MY04 model does not match very well with the official data provided by the department of energy (DOE). It is also found that the original battery model does not consider the impact of environmental temperature on battery cell capacities. To improve battery model, this study includes battery current loss on coulomb coefficient and the impact of environmental temperature on battery cell capacity in the model. In addition, voltage losses on both double layer effect and diffusion effect are included in the new battery model. The simulation results with new battery model show the reduced fuel economy error to the DOE data comparing with the original Autonomie Prius MY04 model.

Electro-oxidation of Au(1 1 1) in contact with aqueous electrolytes: New insight from in situ vibration spectroscopy

We carried out a comprehensive study of Au(1 1 1) oxidation–reduction in the presence of (hydrogen-) sulfate ions on ideally smooth and stepped Au(S)[n(1 1 1)-(1 1 1)] single crystal electrodes using cyclic voltammetry, in situ scanning tunneling microscopy (STM) and vibration spectroscopy, such as surface-enhanced infrared absorption spectroscopy (SEIRAS) and shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). Surface structure changes and the role of surface defects in the potential regions of double layer charging and gold oxidation/reduction are discussed based on cyclic voltammetry and in situ STM data. SEIRAS and SHINERS provide complementary information on the chemical nature of adsorbates. In particular, the potential-dependent formation and stability ranges of adsorbed sulfate, hydroxide-species and of gold surface oxide could be resolved in detail. Based on our experimental observations, we proposed new and extended mechanisms of gold surface oxidation and reduction in 1.0 M H2SO4 and 1.0 M Na2SO4.

Three-State Single-Molecule Naphthalenediimide Switch: Integration of a Pendant Redox Unit for Conductance Tuning

We studied charge transport through core-substituted naphthalenediimide (NDI) single-molecule junctions using the electrochemical STM-based break-junction technique in combination with DFT calculations. Conductance switching among three well-defined states was demonstrated by electrochemically controlling the redox state of the pendent diimide unit of the molecule in an ionic liquid. The electrical conductances of the dianion and neutral states differ by more than one order of magnitude. The potential-dependence of the charge-transport characteristics of the NDI molecules was confirmed by DFT calculations, which account for electrochemical double-layer effects on the conductance of the NDI junctions. This study suggests that integration of a pendant redox unit with strong coupling to a molecular backbone enables the tuning of charge transport through single-molecule devices by controlling their redox states.

Acoustic properties of microperforated panels and their optimizatión by simulated annealing

This thesis investigates the acoustic properties of microperforated panels as an alternative to passive noise control. The first chapters are devoted to the review of analytical models to obtain the acoustic impedance and absorption coefficient of perforated panels. The use of panels perforated with circular holes or with slits is discussed. The theoretical models are presented and some modifications are proposed to improve the modeling of the physical phenomena occurring at the perforations of the panels. The absorption band is widened through the use of multiple layer microperforated panels and/or the combination of a millimetric panel with a porous layer that can be a fibrous material or a nylon mesh. A commercial micrometric mesh downstream a millimetric panel is proposed as a very efficient and low cost solution for controlling noise in reduced spaces. The simulated annealing algorithm is used in order to optimize the panel construction to provide a maximum of absorption in a determined wide band frequency range. Experiments are carried out at normal sound incidence and plane waves. One example is shown for a double layer microperforated panel subjected to grazing flow. A good agreement is achieved between the theory and the experiments. RESUMEN En esta tesis se investigan las propiedades acústicas de paneles micro perforados como una alternativa al control pasivo del ruido. Los primeros capítulos están dedicados a la revisión de los modelos de análisis para obtener la impedancia acústica y el coeficiente de absorción de los paneles perforados. El uso de paneles perforados con agujeros circulares o con ranuras es discutido. Se presentan diferentes modelos y se proponen algunas modificaciones para mejorar la modelización de los fenómenos físicos que ocurren en las perforaciones. La banda de absorción se ensancha a través del uso de capas múltiples de paneles micro perforados y/o la combinación de un panel de perforaciones milimétricas combinado con una capa porosa que puede ser un material fibroso o una malla de nylon. Se propone el uso de una malla micrométrica detrás de un panel milimétrico como una solución económica y eficiente para el control del ruido en espacios reducidos. El algoritmo de recocido simulado se utiliza con el fin de optimizar la construcción de paneles micro perforados para proporcionar un máximo de absorción en una banda determinada frecuencias. Los experimentos se llevan a cabo en la incidencia normal de sonido y ondas planas. Se muestra un ejemplo de panel micro perforado de doble capa sometido a flujo rasante. Se consigue un buen acuerdo entre la teoría y los experimentos.

Estructuras espaciales desmontables y desplegables. Estudio de la obra del arquitecto Emilio Pérez Pinero.

La presente tesis estudia las realizaciones del arquitecto Emilio Pérez Pinero, todas dentro de las estructuras espaciales de barras desmontables y desplegables, elabora la documentación que hace transmisible su investigación y generaliza el estudio del comportamiento en la parcela de las desplegables. La obra de este arquitecto forma un conjunto original, atractivo y sin continuadores, y por otra parte, no abundan las" investigaciones sobre este tipo de estructuras ( mucho menos las realizaciones), en las que hay que resolver tanto su definición como su movilidad y comportamiento estructural. El contenido de la parte correspondiente a las estructuras desmontables se limita a las cúpulas reticuladas de una capa, con el sistema de reticulado y montaje ideado por Pinero, por considerar que se debe documentar su aportación pero no incidir mas en un campo de investigación que cuenta con abundantes estudios. Se aporta la solución matemática y un programa de ordenador para la definición geométrica completa del reticulado empleado. Las estructuras desplegables se caracterizan por el empleo de barras dispuestas en "x" en el espesor de la estructura, con generación de superficies tanto planas como curvas. En ambos casos se analiza la movilidad en fase de mecanismo, tanto a las soluciones de Pinero como a las complementarlas que se exponen. Se estudian las relaciones geométricas que deben de cumplirse para que sea posible el movimiento de las barras, relaciones particularmente complejas en las desplegables según superficies esféricas, y que determinan su definición geométrica. En la fase de estructura, además de analizar lo realizado por Pinero, documentando y definiendo sus componentes, se proponen varias estructuras posibles para cada mecanismo, y se desarrolla en detalle el tipo de los emparrillados de canto constante, donde se incluye un estudio comparativo de nueve variantes distintas. Se muestra el amplio campo de uso posible para estas estructuras. ABSTRACT The • present doctoral dissertation studies the work of de spanish architect Emilio Pérez Pinero, all of it within de field of spatial demountable and deployable structures. This contribution compiles the necessary documentation for research in this field and, besides, generalizes the theoretical background for the analysis of this type of structures. Pérez Pinero's contributions are original and attractive, but, so far, he has not any followers ; on the other hand research in this field is scarce (much less actual realizations). In the part corresponding to demountable structures the research is limited to reticulated domes of only one layer, following Pérez Pinero's sys~ tem, trying to give a comprehensive documentation of it. The mathematical solution is given and so is a computer program for the complete definition of the geometry of the structure. One characteristic of deployable structures is the use of struts placed - formix "X" in the thickness of the structure, making possible the generation of plañe as well as curved surfaces. In both cases, the operation in the phase of mechanism is studied, both fot Pinero's solution and for the other schemes presented. The geometrical relationships that must be maintained in order to guarantee strut's movements, are studied; these relationships are particularly complex in the case of spherical surfaces, and, in this last casey determine completely its geometrical definition. In regard of the structure behaviour, besides analysing Pinero's works, a variety of solutions are proposed for each mechanism. Particularly, the configuration for double layer grids of constant thickness is developed with great detall, and a comparative study of nine different solutions of this special case is included. A wide range of the possible applications of this structural type is shown.

Mutual coupling reduction using EBG in steering antennas

In this letter, a dual circular polarized steering antenna for satellite communications in X-band is presented. This antenna consists of printed elements grouped in an array, able to work from 7.25 up to 8.4 GHz in both polarizations: left-handed circular polarization (LHCP) and right-handed circular polarization (RHCP). The module antenna is compact, with narrow beamwidth, and reaches a gain of 16 dBi. It has the capability to steer in elevation to and electronically with a Butler matrix. In order to reduce the mutual coupling between adjacent patches, electromagnetic band-gap (EBG) structures are introduced. These EBGs combine double-layer and edge location via in order to reduce the size, without changing the low-permittivity substrate, and therefore maintaining the high radiation efficiency of the antenna.

EBG size reduction for low permittivity substrates

Double layer and edge-location via techniques are combined for electromagnetic band gap (EBG) size reduction. The study of the required number of elements and their dimensions is carried out in order to suppress the surface wave propagation modes and consequently to reduce the mutual coupling between radiating elements in low-permittivity substrates. By applying these techniques, the size of the EBG mushroom is reduced by 30%; however, the bandwidth operation maintains its value, and these structures can be integrated between radiating elements in broad bandwidth antennas.

Current collection by an active spherical electrode in an unmagnetized plasma

A theoretical model for the steady-state response of anodic contactors that emit a plasma current Ii and collect electrons from a collisionless, unmagnetized plasma is presented. The use of a (kinetic) monoenergetic population for the attracted species, well known in passive probe theory, gives both accuracy and tractability to the theory. The monoenergetic population is proved to behave like an isentropic fluid with radial plus centripetal motion, allowing direct comparisons with ad hoc fluid models. Also, a modification of the original monoenergetic equations permits analysis of contactors operating in orbit-limited conditions. Besides that, the theory predicts that, only for plasma emissions above certain threshold current a presheath/double layer/core structure for the potential is formed (the core mode), while for emissions below that threshold, a plasma contactor behaves exactly as a positive-ion emitter with a presheath/sheath structure (the no-core mode). Ion emitters are studied as a particular case. Emphasis is placed on obtaining dimensionless charts and approximate asymptotic laws of the current-voltage characteristic.

Bare-tether cathodic contact through thermoionic emission by low work-function materials

A new material, C12A7 : electride, which might present a work function as low as 0.6 eV and moderately high temperature stability, was recently proposed as coating for floating bare tethers. Arising from heating under space operation, current is emitted by thermionic emission along a thus coated cathodic segment. A preliminary study on the space-charge-limited (SCL) double layer in front of the cathodic segment is presented using Langmuir’s SCL electron current between cylindrical electrodes and orbital-motion-limited ion-collection sheath. A detailed calculation of current and bias profiles along the entire tether length is carried out with ohmic effects and the transition from SCL to full Richardson-Dushman emission included. Analysis shows that in the simplest drag mode, under typical orbital and tether conditions, thermionic emission leads to a short cathodic section and may eliminate the need for an active cathodic device and its corresponding gas feed requirements and power subsystem, which results in a truly “propellant-less” tether system for such basic applications as de-orbiting low earth orbit satellites.

Analysis of Magnetic Nozzles For Space Plasma Thrusters = Análisis de Toberas Magnéticas para Motores Espaciales de Plasma

Esta tesis presenta un análisis teórico del funcionamiento de toberas magnéticas para la propulsión espacial por plasmas. El estudio está basado en un modelo tridimensional y bi-fluido de la expansión supersónica de un plasma caliente en un campo magnético divergente. El modelo básico es ampliado progresivamente con la inclusión de términos convectivos dominantes de electrones, el campo magnético inducido por el plasma, poblaciones electrónicas múltiples a distintas temperaturas, y la capacidad de integrar el flujo en la región de expansión lejana. La respuesta hiperbólica del plasma es integrada con alta precisión y eficiencia haciendo uso del método de las líneas características. Se realiza una caracterización paramétrica de la expansión 2D del plasma en términos del grado de magnetización de iones, la geometría del campo magnético, y el perfil inicial del plasma. Se investigan los mecanismos de aceleración, mostrando que el campo ambipolar convierte la energía interna de electrones en energía dirigida de iones. Las corrientes diamagnéticas de Hall, que pueden hallarse distribuidas en el volumen del plasma o localizadas en una delgada capa de corriente en el borde del chorro, son esenciales para la operación de la tobera, ya que la fuerza magnética repulsiva sobre ellas es la encargada de confinar radialmente y acelerar axialmente el plasma. El empuje magnético es la reacción a esta fuerza sobre el motor. La respuesta del plasma muestra la separación gradual hacia adentro de los tubos de iones respecto de los magnéticos, lo cual produce la formación de corrientes eléctricas longitudinales y pone el plasma en rotación. La ganancia de empuje obtenida y las pérdidas radiales de la pluma de plasma se evalúan en función de los parámetros de diseño. Se analiza en detalle la separación magnética del plasma aguas abajo respecto a las líneas magnéticas (cerradas sobre sí mismas), necesaria para la aplicación de la tobera magnética a fines propulsivos. Se demuestra que tres teorías existentes sobre separación, que se fundamentan en la resistividad del plasma, la inercia de electrones, y el campo magnético que induce el plasma, son inadecuadas para la tobera magnética propulsiva, ya que producen separación hacia afuera en lugar de hacia adentro, aumentando la divergencia de la pluma. En su lugar, se muestra que la separación del plasma tiene lugar gracias a la inercia de iones y la desmagnetización gradual del plasma que tiene lugar aguas abajo, que permiten la separación ilimitada del flujo de iones respecto a las líneas de campo en condiciones muy generales. Se evalúa la cantidad de plasma que permanece unida al campo magnético y retorna hacia el motor a lo largo de las líneas cerradas de campo, mostrando que es marginal. Se muestra cómo el campo magnético inducido por el plasma incrementa la divergencia de la tobera magnética y por ende de la pluma de plasma en el caso propulsivo, contrariamente a las predicciones existentes. Se muestra también cómo el inducido favorece la desmagnetización del núcleo del chorro, acelerando la separación magnética. La hipótesis de ambipolaridad de corriente local, común a varios modelos de tobera magnética existentes, es discutida críticamente, mostrando que es inadecuada para el estudio de la separación de plasma. Una inconsistencia grave en la derivación matemática de uno de los modelos más aceptados es señalada y comentada. Incluyendo una especie adicional de electrones supratérmicos en el modelo, se estudia la formación y geometría de dobles capas eléctricas en el interior del plasma. Cuando dicha capa se forma, su curvatura aumenta cuanto más periféricamente se inyecten los electrones supratérmicos, cuanto menor sea el campo magnético, y cuanto más divergente sea la tobera magnética. El plasma con dos temperaturas electrónicas posee un mayor ratio de empuje magnético frente a total. A pesar de ello, no se encuentra ninguna ventaja propulsiva de las dobles capas, reforzando las críticas existentes frente a las propuestas de estas formaciones como un mecanismo de empuje. Por último, se presenta una formulación general de modelos autosemejantes de la expansión 2D de una pluma no magnetizada en el vacío. El error asociado a la hipótesis de autosemejanza es calculado, mostrando que es pequeño para plumas hipersónicas. Tres modelos de la literatura son particularizados a partir de la formulación general y comparados. Abstract This Thesis presents a theoretical analysis of the operation of magnetic nozzles for plasma space propulsion. The study is based on a two-dimensional, two-fluid model of the supersonic expansion of a hot plasma in a divergent magnetic field. The basic model is extended progressively to include the dominant electron convective terms, the plasma-induced magnetic field, multi-temperature electron populations, and the capability to integrate the plasma flow in the far expansion region. The hyperbolic plasma response is integrated accurately and efficiently with the method of the characteristic lines. The 2D plasma expansion is characterized parametrically in terms of the ion magnetization strength, the magnetic field geometry, and the initial plasma profile. Acceleration mechanisms are investigated, showing that the ambipolar electric field converts the internal electron energy into directed ion energy. The diamagnetic electron Hall current, which can be distributed in the plasma volume or localized in a thin current sheet at the jet edge, is shown to be central for the operation of the magnetic nozzle. The repelling magnetic force on this current is responsible for the radial confinement and axial acceleration of the plasma, and magnetic thrust is the reaction to this force on the magnetic coils of the thruster. The plasma response exhibits a gradual inward separation of the ion streamtubes from the magnetic streamtubes, which focuses the jet about the nozzle axis, gives rise to the formation of longitudinal currents and sets the plasma into rotation. The obtained thrust gain in the magnetic nozzle and radial plasma losses are evaluated as a function of the design parameters. The downstream plasma detachment from the closed magnetic field lines, required for the propulsive application of the magnetic nozzle, is investigated in detail. Three prevailing detachment theories for magnetic nozzles, relying on plasma resistivity, electron inertia, and the plasma-induced magnetic field, are shown to be inadequate for the propulsive magnetic nozzle, as these mechanisms detach the plume outward, increasing its divergence, rather than focusing it as desired. Instead, plasma detachment is shown to occur essentially due to ion inertia and the gradual demagnetization that takes place downstream, which enable the unbounded inward ion separation from the magnetic lines beyond the turning point of the outermost plasma streamline under rather general conditions. The plasma fraction that remains attached to the field and turns around along the magnetic field back to the thruster is evaluated and shown to be marginal. The plasmainduced magnetic field is shown to increase the divergence of the nozzle and the resulting plasma plume in the propulsive case, and to enhance the demagnetization of the central part of the plasma jet, contrary to existing predictions. The increased demagnetization favors the earlier ion inward separation from the magnetic field. The local current ambipolarity assumption, common to many existing magnetic nozzle models, is critically discussed, showing that it is unsuitable for the study of plasma detachment. A grave mathematical inconsistency in a well-accepted model, related to the acceptance of this assumption, is found out and commented on. The formation and 2D shape of electric double layers in the plasma expansion is studied with the inclusion of an additional suprathermal electron population in the model. When a double layer forms, its curvature is shown to increase the more peripherally suprathermal electrons are injected, the lower the magnetic field strength, and the more divergent the magnetic nozzle is. The twoelectron- temperature plasma is seen to have a greater magnetic-to-total thrust ratio. Notwithstanding, no propulsive advantage of the double layer is found, supporting and reinforcing previous critiques to their proposal as a thrust mechanism. Finally, a general framework of self-similar models of a 2D unmagnetized plasma plume expansion into vacuum is presented and discussed. The error associated with the self-similarity assumption is calculated and shown to be small for hypersonic plasma plumes. Three models of the literature are recovered as particularizations from the general framework and compared.

In situ control of the GE(100)surface domain structure for III-V multijunction solar cells

Vicinal Ge(100) is the common substrate for state of the art multi-junction solar cells grown by metal-organic vapor phase epitaxy (MOVPE). While triple junction solar cells based on Ge(100) present efficiencies mayor que 40%, little is known about the microscopic III-V/Ge(100) nucleation and its interface formation. A suitable Ge(100) surface preparation prior to heteroepitaxy is crucial to achieve low defect densities in the III-V epilayers. Formation of single domain surfaces with double layer steps is required to avoid anti-phase domains in the III-V films. The step formation processes in MOVPE environment strongly depends on the major process parameters such as substrate temperature, H2 partial pressure, group V precursors [1], and reactor conditions. Detailed investigation of these processes on the Ge(100) surface by ultrahigh vacuum (UHV) based standard surface science tools are complicated due to the presence of H2 process gas. However, in situ surface characterization by reflection anisotropy spectroscopy (RAS) allowed us to study the MOVPE preparation of Ge(100) surfaces directly in dependence on the relevant process parameters [2, 3, 4]. A contamination free MOVPE to UHV transfer system [5] enabled correlation of the RA spectra to results from UHV-based surface science tools. In this paper, we established the characteristic RA spectra of vicinal Ge(100) surfaces terminated with monohydrides, arsenic and phosphorous. RAS enabled in situ control of oxide removal, H2 interaction and domain formation during MOVPE preparation.