Si and SixGe1-x NWs studied by Raman spectroscopy

Group IV nanostructures have attracted a great deal of attention because of their potential applications in optoelectronics and nanodevices. Raman spectroscopy has been extensively used to characterize nanostructures since it provides non destructive information about their size, by the adequate modeling of the phonon confinement effect. The Raman spectrum is also sensitive to other factors, as stress and temperature, which can mix with the size effects borrowing the interpretation of the Raman spectrum. We present herein an analysis of the Raman spectra obtained for Si and SiGe nanowires; the influence of the excitation conditions and the heat dissipation media are discussed in order to optimize the experimental conditions for reliable spectra acquisition and interpretation.

Raman spectrum of group IV nanowires: influence of temperature

Group IV semiconductor nanowires are characterized by Raman spectroscopy. The results are analyzed in terms of the heating induced by the laser beam on the nanowires. By solving the heat transport equation one can simulate the temperature reached by the NWs under the exposure to a laser beam. The results are illustrated with Si and Si1-xGex nanowires. Both bundles of nanowires and individual nanowires are studied. The main experimental conditions contributing to the nanowire heating are discussed

Raman and infrared spectra of dimethyl ether 13C-isotopologue (CH3O13CH3) from a CCSD(T) potential energy surface

So far, no experimental data of the infrared and Raman spectra of 13C isotopologue of dimethyl ether are available. With the aim of providing some clues of its low-lying vibrational bands and with the hope of contributing in a next spectral analysis, a number of vibrational transition frequencies below 300 cm−1 of the infrared spectrum and around 400 cm−1 of the Raman spectrum have been predicted and their assignments were proposed. Calculations were carried out through an ab initio three dimensional potential energy surface based on a previously reported one for the most abundant dimethyl ether isotopologue (M. Villa et al., J. Phys. Chem. A 115 (2011) 13573). The potential function was vibrationally corrected and computed with a highly correlated CCSD(T) method involving the COC bending angle and the two large amplitude CH3 internal rotation degrees of freedom. Also, the Hamiltonian parameters could represent a support for the spectral characterization of this species. Although the computed vibrational term values are expected to be very accurate, an empirical adjustment of the Hamiltonian has been performed with the purpose of anticipating some workable corrections to any possible divergence of the vibrational frequencies. Also, the symmetry breaking derived from the isotopic substitution of 13C in the dimethyl ether was taken into account when the symmetrization procedure was applied.

Interaction between a laser beam and semiconductor nanowires: application to the raman spectrum of Si nanowires

One presents in this work the study of the interaction between a focused laser beam and Si nanowires (NWs). The NWs heating induced by the laser beam is studied by solving the heat transfer equation by finite element methods (fem). This analysis permits to establish the temperature distribution inside the NW when it is excited by the laser beam. The overheating is dependent on the dimensions of the NW, both the diameter and the length. When performing optical characterization of the NWs using focused laser beams, one has to consider the temperature increase introduced by the laser beam. An important issue concerns the fact that the NWs diameter has subwavelength dimensions, and is also smaller than the focused laser beam. The analysis of the thermal behaviour of the NWs under the excitation with the laser beam permits the interpretation of the Raman spectra of Si NWs, where it is demonstrated that temperature induced by the laser beam play a major role in shaping the Raman spectrum of Si NWs

Interaction between a laser beam and semiconductor nanowires: application to the raman spectrum of Si nanowires

One presents in this work the study of the interaction between a focused laser beam and Si nanowires (NWs). The NWs heating induced by the laser beam is studied by solving the heat transfer equation by finite element methods (FEM). This analysis permits to establish the temperature distribution inside the NW when it is excited by the laser beam. The overheating is dependent on the dimensions of the NW, both the diameter and the length. When performing optical characterisation of NWs using focused laser beams, one has to consider the temperature increase introduced by the laser beam. An important issue concerns the fact that the NW's diameter has subwavelength dimensions, and is also smaller than the focused laser beam. The analysis of the thermal behaviour of the NWs under the excitation with the laser beam permits the interpretation of the Raman spectrum of Si NWs. It is demonstrated that the temperature increase induced by the laser beam plays a major role in shaping the Raman spectrum of Si NWs.

Raman spectroscopy in Group IV nanowires and nanowire axial heterostructures

The control of the SiGe NW composition is fundamental for the fabrication of high quality heterostructures. Raman spectroscopy has been used to analyse the composition of SiGe alloys. We present a study of the Raman spectrum of SiGe nanowires and SiGe/Si heterostructures. The inhomogeneity of the Ge composition deduced from the Raman spectrum is explained by the existence of a Ge-rich outer shell and by the interaction of the NW with the electromagnetic field associated with the laser beam.

Electromagnetic interaction between a laser beam and semiconductor nanowires deposited on different substrates: Raman enhancement in Si Nanowires

Raman scattering of Si nanowires (NWs) presents antenna effects. The electromagnetic resonance depends on the electromagnetic coupling of the system laser/NW/substrate. The antenna effect of the Raman signal was measured in individual NWs deposited on different substrates, and also free standing NWs in air. The one phonon Raman band in NWs can reach high intensities depending on the system configuration; values of Raman intensity per unit volume more than a few hundred times with respect to bulk substrate can be obtainedRaman scattering of Si nanowires (NWs) presents antenna effects. The electromagnetic resonance depends on the electromagnetic coupling of the system laser/NW/substrate. The antenna effect of the Raman signal was measured in individual NWs deposited on different substrates, and also free standing NWs in air. The one phonon Raman band in NWs can reach high intensities depending on the system configuration; values of Raman intensity per unit volume more than a few hundred times with respect to bulk substrate can be obtained

Resolución estructural en 3D de electrocerámicas mediante microscopía Raman confocal

Las propiedades de los materiales cerámicos son una combinación entre las propiedades intrínsecas, definidas por los granos cristalinos, y las propiedades extrínsecas, como son bordes de grano y fases secundarias. La relación entre estos dos elementos produce en muchas ocasiones, la presencia de propiedades inusuales que son la base de muchos materiales electrocerámicos. Sirvan como ejemplo algunos materiales tipo como son: varistores cerámicos, termistores, materiales con coeficiente de resistividad positivo, sensores de borde de grano, etc. En un material electrocerámico con respuesta funcional la correlación entre estructura-microestructura -propiedades es una constante, tanto en la etapa de diseño en laboratorio como en la etapa de producción industrial. El empleo de Microscopía Raman Confocal (MRC) se propone como una metodología relevante para el estudio de los factores que afectan a dichas correlaciones en materiales electrocerámicos. La técnica de MRC constituye una potente herramienta que permite determinar no solo la estructura sino las interacciones entre los elementos microestructurales. La correlación entre estas variables con las propiedades funcionales y la posibilidad de determinar las mismas en condiciones de operación, abren unas posibilidades que hasta la fecha solo estaban en la imaginación de los científicos. En esta presentación se resumen brevemente algunos de los principios relacionados con la técnica de Microscopía Raman Confocal, que junto con ejemplos seleccionados permiten visualizar aspectos relacionados con: la orientación de cristales, identificación fases cristalinas; resolución de nanoestructuras e interfases; determinación y dinámica de dominios ferroeléctricos; presencia de tensiones mecánicas; fenómenos de conducción,... sobre diferentes materiales cerámicos. Los trabajos mostrados son ejemplos de alta resolución en 3D de materiales funcionales como son los materiales electrocerámicos.

Emergencia y convergencia de las corrientes urbanísticas alternativas al desarrollo disperso. Europa y los EE.UU. 1980/2010

La presente tesis doctoral identifica el reciente fenómeno de la emergenciai de corrientes urbanísticas que actúan en la periferia urbana a partir de una concepción del diseño urbano que propugna modelos más compactos, a escala humana, de carácter integral y sostenible, como alternativa al desarrollo disperso y difusoii que caracteriza en gran medida a la ciudad contemporánea. Se develan las diferencias de origen y las coincidencias entre las distintas líneas de pensamiento que definen a estas emergentes corrientes alternativas, situándolas dentro de determinados enfoques planteados en la presente tesis, y demostrando con ello, las progresivas áreas de convergencia que permiten su ordenamiento como fenómeno histórico común. Estas distintas líneas de pensamiento, que derivan en las corrientes urbanísticas alternativas, se manifiestan primeramente como reacción a las operaciones modernistas de la posguerra, pero crecientemente expresan una visión contestataria a la expansión urbana descontrolada iii, de bajas densidades, zonificación excluyente y dependiente del automóvil; modelo asociado a las autopistas urbanas, los llamados nuevos artefactos urbanos y las grandes parcelas destinadas a proyectos habitacionales. Una realidad expresada en variados contextos en el ámbito de la globalización económica y cultural que, en gran medida, se singulariza como responsable de las profundas transformaciones urbanas, de la consecuente gradual pérdida de habitabilidad en las ciudades y del impacto sobre el medio natural; cuestión a tratar en el “Marco conceptual” referido al contexto y problema de la tesis. Se estudian los planteamientos fundamentales que postulan estas corrientes alternativas en el contexto de la expansión urbana horizontal, con el fin de identificar las distintas vertientes o líneas existentes, de establecer sus orígenes, enfoques, vínculos y alcances, permitiendo con ello caracterizar el fenómeno en sí desde una visión original e integradora. Estas corrientes a tratar han surgido en diversos momentos y con diversas particularidades, pero con mayor intensidad, articulación y visibilidad a partir de los años ochenta y especialmente en los noventa del siglo recién pasado, fundamentalmente en Europa y en los Estados Unidos de América, representando el “Cuerpo teórico” de esta tesis. Emergen en un escenario de creciente empoderamiento ciudadano, en tiempos de una mayor conciencia ambiental y social, y desde la convicción extendida de las limitaciones de un desarrollismo que, en términos del territorio físico, se manifiesta en el crecimiento urbano por extensión, incremental y desarticulado; tienen distintos idearios de origen, algunos en aparente contradicción o manifiesta oposición entre sí; se articulan desde diversos énfasis y surgen a partir de distintas aproximaciones. Para poder comprender el fenómeno de manera integral, se identifican y observan las tendencias contemporáneas y las correspondientes corrientes principales del diseño urbano; se indaga en sus discursos críticos y se ordenan en función de tres enfoques, los cuales reúnen los fundamentos esenciales de las distintas miradas críticas al modelo disperso y difuso: el enfoque neotradicional, el enfoque de la movilidad, y el enfoque ecológicoiv. Reconociendo la importancia de las operaciones de renovación urbana en la “ciudad intramuros” y siendo partícipes de estas intervenciones, las diferentes corrientes observadas desde los tres enfoques planteados, tienen un común denominador disciplinar en cuanto a su preocupación por generar actuaciones urbanas viables y practicables que causen un menor impacto sobre el territorio y que ofrezcan las condiciones para mejorar la habitabilidad en la ciudad, asumiendo el crecimiento hacia las periferias desde una aproximación alternativa a los modelos hoy predominantes. Las distintas corrientes, desde los particulares enfoques señalados, pretenden en síntesis, un desarrollo que refuerce el rol del diseño urbano, que promueva modelos más compactosv, de usos mixtos compatibles con la residencia y con espacios públicos de calidad, a una escala apropiada para la movilidad peatonal, favoreciendo de esta manera el uso del transporte público y velando consecuentemente por aquellos aspectos que mejoren las condiciones de sostenibilidad. En definitiva, el ideario de las corrientes caracterizadas en esta tesis como alternativas, se origina y se sostiene a partir de la convicción de situar a la disciplina del diseño urbano en su justa medida en el desarrollo contemporáneo, en el convencimiento de la relevancia del proyecto urbano en el ordenamiento del territorio y el crecimiento de las ciudades actuales. Una convergencia implícita a tratarse en la “Discusión de resultados”. La preocupación que reflejan las distintas corrientes estudiadas por el hábitat construido, en cuanto a su condición de acoger y estimular la dimensión humana de las ciudades, puede resumirse en una cita del arquitecto danés Jan Gehl, que interpreta a muchas de las líneas de pensamiento que se abordan en esta tesis, en cuanto al deseo de crear mejores ciudades: “Aspiramos generar ciudades animadas, saludables, atractivas, sostenibles y seguras, con el propósito de mejorar la calidad de vida de la gente”. ABSTRACT This Ph.D thesis identifies the recent phenomenon of the emergence of alternative urban design currents in the city edge, that focus on a more compact, human-scale oriented, comprehensive and sustainable urban design as an alternative to the overwhelming advance of sprawl that largely characterizes the contemporary city. It singles out the differences in origin, as well as the similarities drawn from the different lines of thought that define these emergent alternative currents, placing them within certain approaches proposed in this thesis, and thereby demonstrating the progressive areas of convergence that allow to arrange them as a common historical phenomenon. Indeed, the different lines of thought that drift towards these alternative urbanistic currents, first appear as a reaction to the post- World War II Modernist housing projects, and increasingly more so as a response to urban sprawl; an ever expanding phenomemnon expressed in different contexts within the economic and cultural globalization, largely singled out as being responsible for the deep urban transformations, the consequent gradual loss of livability and the impact on natural environment, setting the “Conceptual framework” of this thesis. Within the context of urban sprawl, the fundamental principles of these alternative currents are studied to establish their origins, approaches, linkages and scope, in order to zero in on the various aspects or existing lines and thereby allowing the identification of the phenomenon from an original and inclusive vision. The alternative currents to be dealt with, emerged at different times and with diverse characteristics, nonetheless it is in the eighties and especially during the nineties, mainly in Europe and the United States, where they appear with greater intensity, coordination and visibility, representing the “Theoretical body” of this thesis. The above mentioned currents arise in a scenario of increasing citizen empowerment in times of growing environmental and social awareness, along with the widespread conviction of the limitations of a quantitative development expressed as a physical manifestation in urban sprawl. These alternative currents have a different philosophy in origin, some are in apparent contradiction or in definite opposition, being organized from different approaches and emphases. To comprehend this phenomenon, it is necessary to identify and analize the contemporary trends and the main currents of urban design, inquiring and arranging their critical discourses according to three approaches that meet the essential foundations of the various critical perspectives of urban sprawl: the neo-traditional approach, the mobility approach, the ecological approach. Acknowledging the importance of urban renovation in the “Inner City”, and being partakers of these interventions, the different currents identified from these three approaches, concur in their concern for the development of viable and workable alternatives to urban sprawl; models that cause a lower impact on the territory, whilst improving livability in the city. The different currents recognized within the above mentioned approaches, advocate in brief, for a development that strengthens the role of urban design, that encourages more compact models, mixed-uses, and quality public spaces, considering the human scale and walkability; thereby increasing public transport and promoting consequently, the conditions for sustainable development. Ultimately, the philosophy of the so called alternative currents, is based on the belief of placing urban design as a fundamental discipline in contemporary urban development. The concern for the built habitat reflected by the various currents studied, as of their condition to accept and stimulate the human dimension of the city, can be summed up in a quote from Danish architect Jan Gehl, who represents many of the lines of thought addressed, in the belief of creating better cities: “We aspire to create cities that are lively, healthy, attractive, sustainable and safe-and thereby improve people’s quality of life”.