Providing 30Mbit/s to Spain’s final third. -A techno-economic assessment.

Since the Digital Agenda for Europe released the Europe2020 flagship, Member States are looking for ways of fulfilling their agreed commitments to fast and ultrafast internet deployment. However, Europe is not a homogenous reality. The economic, geographic, social and demographic features of each country make it a highly diverse region to develop best practices over Next Generation Access Networks (NGAN) deployments. There are special concerns about NGAN deployments for “the final third”, as referred to the last 25% of the country’s population who, usually, live in rural areas. This paper assesses, through a techno-economic analysis, the access cost of providing over 30 Mbps broadband for the final third of Spain`s population in municipalities, which are classified into area types, referred to as geotypes. Fixed and mobile technologies are compared in order to determine which is the most cost-effective technology for each geotype. The demographic limit for fixed networks (cable, fibre and copper) is also discussed. The assessment focuses on the supply side and the results show the access network cost only. The research completes a previous published assessment (Techno-economic analysis of next generation access networks roll-out. The case of platform competition, regulation and public policy in Spain) by including the LTE scenario. The LTE scenario is dimensioned to provide 30 Mbps (best effort) broadband, considering a network take-up of 25%. The Rocket techno-economic model is used to assess a ten-year study period deployment. Nevertheless, the deployment must start in 2014 and be completed by 2020, in order to fulfil the Digital Agenda’s goals. The feasibility of the deployment is defined as the ability to recoup the investment at the end of the study period. This ability is highly related to network take-up and, therefore, to service adoption. Network deployment in each geotype is compared with the cost of the deployment in the Urban geotype and broadband expected penetration rates for clarity and simplicity. Debating the cost-effective deployments for each geotype, while addressing the Digital Agenda’s goals regarding fast and ultrafast internet, is the main purpose of this paper. At the end of the last year, the independent Spanish regulation agency released the Spain broadband coverage report at the first half of 2013. This document claimed that 59% and 52% of Spain’s population was already covered by NGAN capable of providing 30 Mbps and 100 Mbps broadband respectively. HFC, with 47% of population coverage, and FTTH, with 14%, were considered as a 100 Mbps capable NGAN. Meanwhile VDSL, with 12% of the population covered, was the only NGAN network considered for the 30 Mbps segment. Despite not being an NGAN, the 99% population coverage of HSPA networks was also noted in the report. Since mobile operators are also required to provide 30 Mbps broadband to 90% of the population in rural areas by the end of 2020, mobile networks will play a significant role on the achievement of the 30 Mbps goal in Spain’s final third. The assessment indicates the cost of the deployment per cumulative households coverage with 4 different NGANs: FTTH, HFC, VDSL and LTE. Research shows that an investment ranging from €2,700 (VDSL) to €5,400 (HFC) million will be needed to cover the first half of the population with any fixed technology assessed. The results state that at least €3,000 million will be required to cover these areas with the least expensive technology (LTE). However, if we consider the throughput that fixed networks could provide and achievement of the Digital Agenda’s objectives, fixed network deployments are recommended for up to 90% of the population. Fibre and cable deployments could cover up to a maximum of 88% of the Spanish population cost efficiently. As there are some concerns about the service adoption, we recommend VDSL and mobile network deployments for the final third of the population. Despite LTE being able to provide the most economical roll-out, VDSL could also provide 50 Mbps from 75% to 90% of the Spanish population cost efficiently. For this population gap, facility based competition between VDSL providers and LTE providers must be encouraged. Regarding 90% to 98.5% of the Spanish population, LTE deployment is the most appropriate. Since costumers in less populated the municipalities are more sensitive to the cost of the service, we consider that a single network deployment could be most appropriate. Finally, it has become clear that it is not possible to deliver 30Mbps to the final 1.5% of the population cost-efficiently and adoption predictions are not optimistic either. As there are other broadband alternatives able to deliver up to 20 Mbps, in the authors’ opinion, it is not necessary to cover the extreme rural areas, where public financing would be required.

Thermoelectric assessment of laser peening induced effects on a metallic biomedical Ti6Al4V

Laser peening has recently emerged as a useful technique to overcome detrimental effects associated to another well-known surface modification processes such as shot peening or grit blasting used in the biomedical field. It is worth to notice that besides the primary residual stress effect, thermally induced effects might also cause subtle surface and subsurface microstructural changes that might influence corrosion resistance. Moreover, since maximum loads use to occur at the surface, they could also play a critical role in the fatigue strength. In this work, plates of Ti-6Al-4V alloy of 7 mm in thickness were modified by laser peening without using a sacrificial outer layer. Irradiation by a Q-switched Nd-YAG laser (9.4 ns pulse length) working in fundamental harmonic at 2.8 J/pulse and with water as confining medium was used. Laser pulses with a 1.5 mm diameter at an equivalent overlapping density (EOD) of 5000 cm-2 were applied. Attempts to analyze the global induced effects after laser peening were addressed by using the contacting and non-contacting thermoelectric power (TEP) techniques. It was demonstrated that the thermoelectric method is entirely insensitive to surface topography while it is uniquely sensitive to subtle variations in thermoelectric properties, which are associated with the different material effects induced by different surface modification treatments. These results indicate that the stress-dependence of the thermoelectric power in metals produces sufficient contrast to detect and quantitatively characterize regions under compressive residual stress based on their thermoelectric power contrast with respect to the surrounding intact material. However, further research is needed to better separate residual stress effects from secondary material effects, especially in the case of low-conductivity engineering materials like titanium alloys.

New strategies in laser processing of TCOs for light management improvement in thin-film silicon solar cells

Light confinement strategies play a crucial role in the performance of thin-film (TF) silicon solar cells. One way to reduce the optical losses is the texturing of the transparent conductive oxide (TCO) that acts as the front contact. Other losses arise from the mismatch between the incident light spectrum and the spectral properties of the absorbent material that imply that low energy photons (below the bandgap value) are not absorbed, and therefore can not generate photocurrent. Up-conversion techniques, in which two sub-bandgap photons are combined to give one photon with a better matching with the bandgap, were proposed to overcome this problem. In particular, this work studies two strategies to improve light management in thin film silicon solar cells using laser technology. The first one addresses the problem of TCO surface texturing using fully commercial fast and ultrafast solid state laser sources. Aluminum doped Zinc Oxide (AZO) samples were laser processed and the results were optically evaluated by measuring the haze factor of the treated samples. As a second strategy, laser annealing experiments of TCOs doped with rare earth ions are presented as a potential process to produce layers with up-conversion properties, opening the possibility of its potential use in high efficiency solar cells.

Interconexión monolítica de módulos fotovoltaicos de silicio amorfo en lámina delgada sobre vidrio mediante ablación láser en régimen de nanosegundos

Esta tesis se centra en el estudio de una secuencia de procesos basados en la tecnología láser y ejecutados en dispositivos fotovoltaicos, que son imprescindibles para el desarrollo en general de las tecnologías fotovoltaicas basadas en lámina delgada y, en particular, de aquellas que utilizan silicio amorfo como absorbente, así como en aplicaciones posteriores de estas tecnologías de alto valor añadido como es la integración arquitectónica de este tipo de dispositivos. En gran parte de las tecnologías FV de lámina delgada, y muy particularmente en la de silicio amorfo, el material se deposita sobre un substrato en un área lo suficientemente grande para que se requiera de un proceso de subdivisión del dispositivo en células de tamaño adecuado, y su posterior conexión en serie para garantizar las figuras eléctricas nominales del dispositivo. Este proceso se ha desarrollado industrialmente hace años, pero no ha habido un esfuerzo científico asociado que permitiera conocer en profundidad los efectos que los procesos en si mismos tiene de forma individualizada sobre los materiales que componen el dispositivo y sus características finales. Este trabajo, desarrollado durante años en el Centro Láser de la UPM, en estrecha colaboración con Centro de Investigaciones Energéticas y Medioambientales (CIEMAT), la Universidad de Barcelona (UB), y la Universidad Politécnica de Cataluña (UPC), se centra justamente en un estudio detallado de dichos procesos, denominados habitualmente P1, P2, P3 y P4 atendiendo al orden en el que se realizan en el dispositivo. Este estudio incluye tanto la parametrización de los procesos, el análisis del efecto que los mismos producen sobre los materiales que componen el dispositivo y su comportamiento fotoeléctrico final, así como la evaluación del potencial uso de fuentes láser de última generación (ultrarrápidas) frente al estándar industrial en la actualidad que es el empleo de fuentes láser convencionales de ancho temporal en el rango de los nanosegundos. En concreto se ha estudiado en detalle las ventajas y limitaciones del uso de sistemas con diferentes rangos espectrales (IR, VIS y UV) y temporales (nanosegundos y picosegundos) para diferentes tipos de configuraciones y disposiciones tecnológicas (entendiendo por estas las habituales configuraciones en substrato y superestrato de este tipo de dispositivos). La caracterización individual de los procesos fue realizada primeramente en células de laboratorio específicamente diseñadas, abriendo nuevos planteamientos y conceptos originales para la mejora de los procesos láser de interconexión y posibilitando el empleo y desarrollo de técnicas y métodos avanzados de caracterización para el estudio de los procesos de ablación en las distintas láminas que conforman la estructura de los dispositivos fotovoltaicos, por lo que se considera que este trabajo ha propuesto una metodología completamente original, y que se ha demostrado efectiva, en este ámbito. Por último el trabajo aborda un tema de particular interés, como es el posible uso de los procesos desarrollados, no para construir los módulos fotovoltaicos en sí, sino para personalizarlos en forma y efectos visuales para potenciar su uso mediante elementos integrables arquitectónicamente, lo que es un ámbito de gran potencial de desarrollo futuro de las tecnologías fotovoltaicas de lámina delgada. En concreto se presentan estudios de fabricación de dispositivos integrables arquitectónicamente y plenamente funcionales no solo en dispositivos de silicio amorfo con efectos de transparencias y generación de formas libres, si no que también se incluye la posibilidad de hacer tales dispositivos con células de silicio cristalino estándar que es la tecnología fotovoltaica de mayor presencia en mercado. Es importante, además, resaltar que la realización de este trabajo ha sido posible gracias a la financiación obtenida con dos proyectos de investigación aplicada, MICROSIL (PSE-120000-2008-1) e INNDISOL (IPT-420000-2019-6), y los correspondientes al Plan Nacional de I+D+I financiados por el ministerio de Ciencia e Innovación y el Ministerio de Economía y Competitividad: CLÁSICO (ENE 2007- 67742-C04-04) y AMIC ENE2010-21384-C04-02. De hecho, y en el marco de estos proyectos, los resultados de este trabajo han ayudado a conseguir algunos de los hitos más importantes de la tecnología fotovoltaica en nuestro país en los últimos años, como fue en el marco de MICROSIL la fabricación del primer módulo de silicio amorfo con tecnología íntegramente española (hecho en colaboración con el CIEMAT), o la fabricación de los dispositivos para integración arquitectónica con geometrías libres que se describen en esta Tesis y que fueron parte de los desarrollos del proyecto INNDISOL. ABSTRACT This thesis focuses on the study of a sequence of laser-based technology and processes executed in photovoltaic devices, which are essential for the overall development of photovoltaic technologies based on thin film and, in particular, those using amorphous silicon as absorbent and subsequent applications of these technologies with high added value such as the architectural integration of such devices. In much of the PV thin film technologies, and particularly in the amorphous silicon material is deposited on a substrate in an area large enough so that it requires a process of subdivision of the device in cells of appropriate size, and subsequent serial connection to ensure nominal device power figures. This process has been industrially developed years ago, but there has been an associate scientific effort that would learn more about the effects that the processes themselves have either individually on the materials that make up the device and its final characteristics. This work, developed over years in the Laser Center of the UPM, in close collaboration with Centre for Energy and Environmental Research (CIEMAT), the University of Barcelona (UB) and the Polytechnic University of Catalonia (UPC)., Focuses precisely in a detailed study of these processes, usually they called P1, P2, P3 and P4 according to the order in which they perform on the device. This study includes both the parameters of the processes, the analysis of the effect they produce on the materials making up the device and its final photoelectric behavior as well as the potential use of EVALUATION of next-generation laser sources (ultrafast) versus standard industry today is the use of conventional laser sources temporal width in the range of nanoseconds. In particular we have studied in detail the advantages and limitations of using systems with different spectral ranges (IR, UV and VIS) and time (nanosecond and picosecond) for different configurations and technological provisions (meaning these typical configurations in substrate and superstrate such devices). Individual characterization of the processes was conducted primarily in laboratory cells specifically designed, opening new approaches and original concepts for improving laser interconnection processes and enabling the use and development of advanced techniques and characterization methods for studying the processes ablation in the different sheets making up the structure of the photovoltaic devices, so it is considered that this work has proposed a completely original methodology, which has proven effective in this area. Finally, the paper addresses a topic of particular interest, as is the possible use of lso developed processes, not to build the photovoltaic modules themselves but to customize fit and visual effects to enhance their use by integrated architectural elements, which is an area of great potential for future development of thin film photovoltaic technologies. Specifically studies manufacture of integrated architecturally and fully functional not only in amorphous silicon devices with transparency effects and generating freeform devices occur, if not also include the ability to make such devices with cells of standard crystalline silicon photovoltaic technology is more visible in the market. It is also important to note that the completion of this work has been possible thanks to the financing obtained with two applied research projects, Microsil (PSE-120000- 2008-1) and INNDISOL (IPT-420000-2019-6), and those for the National R & D funded by the Ministry of Science and Innovation and the Ministry of Economy and Competitiveness: CLASSIC (ENE 2007-67742-C04-04) and AMIC ENE2010-21384-C04- 02. In fact, within the framework of these projects, the results of this work have helped get some of the most important milestones of photovoltaic technology in our country in recent years, as it was under Microsil making the first module Amorphous silicon technology with entirely Spanish (made in collaboration with CIEMAT), or the manufacture of devices for architectural integration with free geometries that are described in this thesis and that were part of the project Inndisol developments.

Análisis prospectivo del despliegue de redes de comunicaciones móviles LTE en nuevas bandas de frecuencia mediante el desarrollo de modelos tecnoeconómicos

El estándar LTE se ha posicionado como una de las claves para que los operadores de telecomunicación puedan abordar de manera eficiente en costes el crecimiento de la demanda de tráfico móvil que se prevé para los próximos años, al ser una tecnología más escalable en el núcleo de la red y más flexible en la interfaz radio que sus predecesoras. En este sentido, es necesario también que los reguladores garanticen un acceso al espectro radioeléctrico adecuado, equitativo y no discriminatorio, que permita un entorno estable para el despliegue de redes de comunicaciones móviles avanzadas. Además de la flexibilización del marco regulador del espectro radioeléctrico en Europa, que ha permitido el despliegue de nuevas tecnologías en las bandas de frecuencia históricas de GSM, se ha puesto a disposición espectro adicional para sistemas IMT en nuevas bandas de frecuencia, lo que ha planteando a su vez nuevos retos para la tecnología y la regulación. La fragmentación del espectro disponible para comunicaciones móviles ha impulsado el desarrollo de técnicas de agregación de portadoras en las nuevas versiones del estándar LTE, que permiten explotar mejor los recursos radio en su conjunto. No obstante, el espectro inferior a 1 GHz sigue siendo escaso, ya que el tráfico móvil aumenta y la banda de 900 MHz aún se utiliza para servicios GSM, lo que no ha conseguido sino agravar la disputa entre los servicios de radiodifusión terrestre y de comunicaciones móviles por la parte superior de la banda UHF. En concreto, la banda de 700 MHz se perfila como una de las próximas para aumentar el espectro disponible para los servicios en movilidad, si bien su liberación por parte de las actuales redes de Televisión Digital Terrestre presenta no pocas dificultades en los Estados miembros en los que ésta es la principal plataforma audiovisual de acceso gratuito, abriendo un debate sobre el modelo audiovisual a largo plazo en Europa. Por otro lado, las políticas públicas de promoción del acceso a la banda ancha rápida y ultrarrápida de la presente década han establecido objetivos ambiciosos para el año 2020, tanto en el ámbito europeo como en los diferentes Estados miembros. La universalización del acceso a redes de banda ancha de al menos 30 Mbps constituye uno de los principales retos. Las expectativas generadas por la tecnología LTE y la puesta a disposición de nuevas bandas de frecuencia hace posible que los servicios de acceso fijo inalámbrico adquieran especial relevancia ante los objetivos de política pública establecidos que, como ha sido reconocido en diversas ocasiones, no podrán lograrse sino con un compendio de diferente tecnologías. Para esta Tesis Doctoral se han desarrollado una serie modelos tecnoeconómicos con el objetivo de realizar un análisis prospectivo que evalúa tres casos de especial relevancia en el despliegue de redes LTE: en primer lugar, la valoración económica de la banda de 700 MHz; en segundo lugar, la evaluación de modelos de negocio y reducción de costes considerando tecnologías femtocelulares; y finalmente, la viabilidad de las redes LTE de acceso fijo inalámbrico para el cierre de la brecha digital en el acceso a la banda ancha de 30 Mbps. En relación con la aplicación del análisis tecnoeconómico para la valoración del espectro de 700 MHz, los resultados obtenidos ponen de manifiesto dos cuestiones fundamentales. En primer lugar, la necesidad de asignar a los operadores más espectro para satisfacer las previsiones de demanda de tráfico móvil a medio plazo. En segundo, existe una diferencia notable en los costes de despliegue de una red LTE cuando se dispone de espectro en frecuencias inferiores a 1 GHz y cuando no, pero esta diferencia de costes disminuye a medida que se añade nuevo espectro sub-1GHz. De esta manera, la atribución de la banda de 700 MHz a servicios de comunicaciones móviles supone una reducción relevante en los costes de despliegue si el operador no dispone de espectro en la banda de 800 MHz, pero no así si ya dispone de espectro en bandas bajas para el despliegue. En este sentido, puede concluirse que el precio que los operadores estarán dispuestos a pagar por el espectro de la banda de 700 MHz dependerá de si ya tienen disponible espectro en la banda de 800 MHz. Sin embargo, dado que la competencia por ese espectro será menor, los ingresos esperables en las licitaciones de esta nueva banda serán en general menores, a pesar de que para algunos operadores este espectro sería tan valioso como el de 800 MHz. En segundo lugar, en relación con el despliegue de femtoceldas pueden extraerse algunas conclusiones en términos de ahorro de costes de despliegue y también de cara a la viabilidad de los modelos de negocio que posibilitan. El ahorro que supone la introducción de femtoceldas en el despliegue de una red LTE frente al caso de un despliegue exclusivamente macrocelular se ha demostrado que es mayor cuanto menor es el ancho de banda disponible para la red macrocelular. En esta línea, para un operador convergente el despliegue de femtoceldas tiene sentido económico si el ancho de banda disponible es escaso (en torno a 2x10 MHz), que, en el caso de España, puede reflejar el caso de los operadores del segmento fijo que son nuevos entrantes en el móvil. Por otro lado, los modelos de acceso abierto son interesantes para operadores exclusivamente móviles, porque consiguen flexibilizar los costes sustituyendo estaciones base macrocelulares por el despliegue de femtoceldas, pero necesitan desplegarse en zonas con una densidad de población relativamente elevada para que éstas descarguen tráfico de varios usuarios de la red macrocelular simultáneamente. No obstante, las femtoceldas son beneficiosas en todo caso si es el usuario quien asume los costes de la femtocelda y el backhaul, lo que sólo parece probable si se integran en el modelo de negocio de comercialización de nuevos servicios. Por tanto, el despliegue de femtoceldas en buena parte de la casuística estudiada sólo tiene sentido si consiguen aumentar los ingresos por usuario comercializando servicios de valor añadido que necesiten calidad de servicio garantizada y exploten a la vez de esa forma su principal ventaja competitiva respecto a la tecnología WiFi. Finalmente, en relación con el papel de la tecnología LTE para la provisión de servicios de acceso fijo inalámbrico para la banda ancha de 30 Mbps, se ha desarrollado un modelo TD-LTE y mediante la metodología de análisis tecnoeconómico se ha realizado un estudio prospectivo para el caso de España. Los resultados obtenidos preciden una huella de cobertura de FTTH del 74% para 2020, y demuestran que una red TD-LTE en la banda de 3,5 GHz resulta viable para aumentar la cobertura de servicios de 30 Mbps en 14 puntos porcentuales. Junto con la consideración de la cobertura de otras redes, la cobertura de 30 Mbps de acuerdo a la viabilidad de los despliegues alcanzaría el 95% en España en el año 2020. Como resumen, los resultados obtenidos muestran en todos los casos la capacidad de la tecnología LTE para afrontar nuevos desafíos en relación con el aumento del tráfico móvil, especialmente crítico en las zonas más urbanas, y el cierre de la brecha digital en el acceso a la banda ancha rápida en las zonas más rurales. ABSTRACT The LTE standard has been pointed out as one of the keys for telecom operators to address the demand growth in mobile traffic foreseen for the next years in a cost-efficient way, since its core network is more scalable and its radio interface more flexible than those of its predecessor technologies. On the other hand, regulators need to guarantee an adequate, equitable and non-discriminatory access to radio spectrum, which enable a favorable environment for the deployment of advanced mobile communication networks. Despite the reform of the spectrum regulatory framework in Europe, which allowed for the deployment of new technologies in the historic GSM bands, additional spectrum has been allocated to IMT systems in new frequency bands, what in turn has set out new challenges for technology and regulation. The current fragmentation of available spectrum in very different frequency bands has boosted the development of carrier aggregation techniques in most recent releases of the LTE standard, which permit a better exploitation of radio resources as a whole. Nonetheless, spectrum below 1 GHz is still scarce for mobile networks, since mobile traffic increases at a more rapid pace than spectral efficiency and spectrum resources. The 900 MHz frequency band is still being used for GSM services, what has worsen the dispute between mobile communication services and terrestrial broadcasting services for the upper part of the UHF band. Concretely, the 700 MHz frequency band has been pointed out as one of the next bands to be allocated to mobile in order to increase available spectrum. However, its release by current Digital Terrestrial Television networks is challenging in Member States where it constitutes the main free access audiovisual platform, opening up a new debate around the audiovisual model in the long term in Europe. On the other hand, public policies of the present decade to promote fast and ultrafast broadband access has established very ambitious objectives for the year 2020, both at European and national levels. Universalization of 30 Mbps broadband access networks constitutes one of the main challenges. Expectations raised by LTE technology and the allocation of new frequency bands has lead fixed wireless access (FWA) services to acquire special relevance in light of public policy objectives, which will not be met but with a compendium of different technologies, as different involved stakeholders have acknowledged. This PhD Dissertation develops techno-economic models to carry out a prospective analysis for three cases of special relevance in LTE networks’ deployment: the spectrum pricing of the 700 MHz frequency band, an assessment of new business models and cost reduction considering femtocell technologies, and the feasibility of LTE fixed wireless access networks to close the 30 Mbps broadband access gap in rural areas. In the first place and regarding the application of techno-economic analysis for 700 MHz spectrum pricing, obtained results reveal two core issues. First of all, the need to allocate more spectrum for operators in order to fulfill mobile traffic demand in the mid-term. Secondly, there is a substantial difference in deployment costs for a LTE network when there is sub-1GHz spectrum available and when there is not, but this difference decreases as additional sub-1GHz spectrum is added. Thus, the allocation of 700 MHz band to mobile communication services would cause a relevant reduction in deployment costs if the operator does not count on spectrum in the 800 MHz, but not if it already has been assigned spectrum in low frequencies for the deployment. In this regard, the price operators will be willing to pay for 700 MHz spectrum will depend on them having already spectrum in the 800 MHz frequency band or not. However, since competition for the new spectrum will not be so strong, expected incomes from 700 MHz spectrum awards will be generally lower than those from the digital dividend, despite this spectrum being as valuable as 800 MHz spectrum for some operators. In the second place, regarding femtocell deployment, some conclusions can be drawn in terms of deployment cost savings and also with reference to the business model they enable. Savings provided by a joint macro-femto LTE network as compared to an exclusively macrocellular deployment increase as the available bandwidth for the macrocells decreases. Therefore, for a convergent operator the deployment of femtocells can only have economic sense if the available bandwidth is scarce (around 2x10 MHz), which might be the case of fix market operators which are new entrant in mobile market. Besides, open access models are interesting for exclusively mobile operators, since they make costs more flexible by substituting macrocell base stations by femtocells, but they need to be deployed relatively densely populated areas so that they can offload traffic from several macrocell users simultaneously. Nonetheless, femtocells are beneficial in all cases if the user assumes both femtocell and backhaul costs, which only seems probable if they are integrated in a business model commercializing new services. Therefore, in many of the cases analyzed femtocell deployment only makes sense if they increase revenues per user through new added value services which need from guaranteed quality of service, thus exploiting its main competitive advantage compared to WiFi. Finally, regarding the role of LTE technology in the provision of fixed wireless access services for 30 Mbps broadband, a TD-LTE model has been developed and a prospective study has been carried out through techno-economic methodology for the Spanish case. Obtained results foresee a FTTH coverage footprint of 74% households for 2020, and prove that a TD-LTE network in the 3.5 GHz band results feasible to increase 30 Mbps service coverage in additional 14 percentage points. To sum up, obtained results show LTE technology capability to address new challenges regarding both mobile traffic growth, particularly critical in urban zones, and the current digital divide in fast broadband access in most rural zones.

A peptide that inhibits hydroxyapatite growth is in an extended conformation on the crystal surface

Proteins play an important role in the biological mechanisms controlling hard tissue development, but the details of molecular recognition at inorganic crystal interfaces remain poorly characterized. We have applied a recently developed homonuclear dipolar recoupling solid-state NMR technique, dipolar recoupling with a windowless sequence (DRAWS), to directly probe the conformation of an acidic peptide adsorbed to hydroxyapatite (HAP) crystals. The phosphorylated hexapeptide, DpSpSEEK (N6, where pS denotes phosphorylated serine), was derived from the N terminus of the salivary protein statherin. Constant-composition kinetic characterization demonstrated that, like the native statherin, this peptide inhibits the growth of HAP seed crystals when preadsorbed to the crystal surface. The DRAWS technique was used to measure the internuclear distance between two 13C labels at the carbonyl positions of the adjacent phosphoserine residues. Dipolar dephasing measured at short mixing times yielded a mean separation distance of 3.2 ± 0.1 Å. Data obtained by using longer mixing times suggest a broad distribution of conformations about this average distance. Using a more complex model with discrete α-helical and extended conformations did not yield a better fit to the data and was not consistent with chemical shift analysis. These results suggest that the peptide is predominantly in an extended conformation rather than an α-helical state on the HAP surface. Solid-state NMR approaches can thus be used to determine directly the conformation of biologically relevant peptides on HAP surfaces. A better understanding of peptide and protein conformation on biomineral surfaces may provide design principles useful for the modification of orthopedic and dental implants with coatings and biological growth factors that are designed to enhance biocompatibility with surrounding tissue.

Highly sensitive biological and chemical sensors based on reversible fluorescence quenching in a conjugated polymer

The fluorescence of a polyanionic conjugated polymer can be quenched by extremely low concentrations of cationic electron acceptors in aqueous solutions. We report a greater than million-fold amplification of the sensitivity to fluorescence quenching compared with corresponding “molecular excited states.” Using a combination of steady-state and ultrafast spectroscopy, we have established that the dramatic quenching results from weak complex formation [polymer(−)/quencher(+)], followed by ultrafast electron transfer from excitations on the entire polymer chain to the quencher, with a time constant of 650 fs. Because of the weak complex formation, the quenching can be selectively reversed by using a quencher-recognition diad. We have constructed such a diad and demonstrate that the fluorescence is fully recovered on binding between the recognition site and a specific analyte protein. In both solutions and thin films, this reversible fluorescence quenching provides the basis for a new class of highly sensitive biological and chemical sensors.

DNA typing in thirty seconds with a microfabricated device

We report the development of a practical ultrafast allelic profiling assay for the analysis of short tandem repeats (STRs) by using a highly optimized microfluidic electrophoresis device. We have achieved baseline-resolved electrophoretic separations of single-locus STR samples in 30 sec. Analyses of PCR samples containing the four loci CSF1PO, TPOX, THO1, and vWA (abbreviated as CTTv) were performed in less than 2 min. This constitutes a 10- to 100-fold improvement in speed relative to capillary or slab gel systems. The separation device consists of a microfabricated channel 45 μm × 100 μm in cross section and 26 mm in length, filled with a replaceable polyacrylamide matrix operated under denaturing conditions at 50°C. A fluorescently labeled STR ladder was used as an internal standard for allele identification. Samples were prepared by standard procedures and only 4 μl was required for each analysis. The device is capable of repetitive operation and is suitable for automated high-speed and high-throughput applications.

The two-dimensional IR nonlinear spectroscopy of a cyclic penta-peptide in relation to its three-dimensional structure

A form of two-dimensional (2D) vibrational spectroscopy, which uses two ultrafast IR laser pulses, is used to examine the structure of a cyclic penta-peptide in solution. Spectrally resolved cross peaks occur in the off-diagonal region of the 2D IR spectrum of the amide I region, analogous to those in 2D NMR spectroscopy. These cross peaks measure the coupling between the different amide groups in the structure. Their intensities and polarizations relate directly to the three-dimensional structure of the peptide. With the help of a model coupling Hamiltonian, supplemented by density functional calculations, the spectra of this penta-peptide can be regenerated from the known solution phase structure. This 2D-IR measurement, with an intrinsic time resolution of less than 1 ps, could be used in all time regimes of interest in biology.

Femtosecond dynamics of DNA-mediated electron transfer

Diverse biophysical and biochemical studies have sought to understand electron transfer (ET) in DNA in part because of its importance to DNA damage and its repair. However, the dynamics and mechanisms of the elementary processes of ET in this medium are not fully understood and have been heavily debated. Two fundamental issues are the distance over which charge is transported and the time-scale on which the transport through the π-stack of the DNA base pairs may occur. With femtosecond resolution, we report direct observation in DNA of ultrafast ET, initiated by excitation of tethered ethidium (E), the intercalated electron acceptor (A); the electron donor (D) is 7-deazaguanine (Z), a modified base, placed at different, fixed distances from A. The ultrafast ET between these reactants in DNA has been observed with time constants of 5 ps and 75 ps and was found to be essentially independent of the D–A separation (10–17 Å). However, the ET efficiency does depend on the D–A distance. The 5-ps decay corresponds to direct ET observed from 7-deazaguanine but not guanine to E. From measurements of orientation anisotropies, we conclude that the slower 75-ps process requires the reorientation of E before ET, similar to E/nucleotide complexes in water. These results reveal the nature of ultrafast ET and its mechanism: in DNA, ET cannot be described as in proteins simply by a phenomenological parameter, β. Instead, the involvement of the base pairs controls the time scale and the degree of coherent transport.

Intermolecular and Intramolecular Charge Transfer in Functional Molecular Materials

This thesis is devoted to the investigation of inter and intramolecular charge transfer (CT) in molecular functional materials and specifically organic dyes and CT crystals. An integrated approach encompassing quantum-chemical calculations, semiempirical tools, theoretical models and spectroscopic measurements is applied to understand structure-property relationships governing the low-energy physics of these materials. Four main topics were addressed: 1) Spectral properties of organic dyes. Charge-transfer dyes are constituted by electron donor (D) and electron acceptor (A) units linked through bridge(s) to form molecules with different symmetry and dimensionality. Their low-energy physics is governed by the charge resonance between D and A groups and is effectively described by a family of parametric Hamiltonians known as essential-state models. These models account for few electronic states, corresponding to the main resonance structures of the relevant dye, leading to a simple picture that is completed introducing the coupling of the electronic system to molecular vibrations, treated in a non-adiabatic way, and an effective classical coordinate, describing polar solvation. In this work a specific essential-state model was proposed and parametrized for the dye Brilliant Green. The central issue in this work has been the definition of the diabatic states, a not trivial task for a multi-branched chromophore. In a second effort, we have used essential-state models for the description of the early-stage dynamics of excited states after ultrafast excitation. Crucial to this work is the fully non-adiabatic treatment of the coupled electronic and vibrational motion, allowing for a reliable description of the dynamics of systems showing a multistable, broken-symmetry excited state. 2) Mixed-stack CT salts. Mixed-stack (MS) CT crystals are an interesting class of multifunctional molecular materials, where D and A molecules arrange themselves to form stacks, leading to delocalized electrons in one dimension. The interplay between the intermolecular CT, electrostatic interactions, lattice phonons and molecular vibrations leads to intriguing physical properties that include (photoinduced) phase transitions, multistability, antiferromagnetism, ferroelectricity and potential multiferroicity. The standard microscopic model to describe this family of materials is the Modified Hubbard model accounting for electron-phonon coupling (Peierls coupling), electron-molecular vibrations coupling (Holstein coupling) and electrostatic interactions. We adopt and validate a method, based on DFT calculations on dimeric DA structures, to extract relevant model parameters. The approach offers a powerful tool to shed light on the complex physics of MS-CT salts. 3) Charge transfer in organic radical dipolar dyes. In collaboration with the group of Prof. Jaume Veciana (ICMAB- Barcellona), we have studied spectral properties of a special class of CT dyes with D-bridge-A structure where the acceptor group is a stable radical (of the perchlorotriphenylmethyl, PTM, family), leading to an open-shell CT dyes. These materials are of interest since they associate the electronic and optical properties of CT dyes with magnetic properties from the unpaired electron. The first effort was devoted to the parametrization of the relevant essential-state model. Two strategies were adopted, one based on the calculation of the low-energy spectral properties, the other based on the variation of ground state properties with an applied electric field. 4) The spectral properties of organic nanoparticles based on radical species are investigated in collaboration with Dr. I. Ratera (ICMAB- Barcellona). Intriguing spectroscopic behavior was observed pointing to the presence of excimer states. In an attempt to rationalize these findings, extensive calculations (TD-DFT and ZINDO) were performed. The results for the isolated dyes are validated against experimental spectra in solution. To address intermolecular interactions we studied dimeric structures in the gas phase, but the preliminary results obtained do not support excimer formation.

Estudo da microestrutura e dinâmica molecular do Poly(3-(2\'-ethylhexyl)thiophene)(P3EHT) via ressonância magnética nuclear

O estudo da microestrutura e dinâmica molecular de polímeros conjugados é de grande importância para o entendimento das propriedades físicas desta classe de materiais. No presente trabalho utilizou-se técnicas de ressonância magnética nuclear em baixo e alto campo para elucidar os processos de dinâmica molecular e cristalização do polímero Poly(3-(2’-ethylhexyl)thiophene) - P3EHT. O P3EHT é um polímero modelo para tal estudo, pois apresenta temperatura de fusão bem inferior a sua temperatura de degradação. Esta característica permite acompanhar os processos de cristalização in situ utilizando RMN. Além disso, sua similaridade ao já popular P3HT o torna um importante candidato a camada ativa em dispositivos eletrônicos orgânicos. O completo assinalamento do espectro de 13C para o P3EHT foi realizado utilizando as técnicas de defasamento dipolar e HETCOR. Os processos de dinâmica molecular, por sua vez, foram sondados utilizando DIPSHIFT. Observou-se um gradiente de mobilidade na cadeia lateral do polímero. Além disso, os baixos valores de parametros de ordem obtidos em comparação a experimentos similares realizados no P3HT na literatura indicam um aparente aumento no volume livre entre cadeias consecutivas na fase cristalina. Isso indica que a presença do grupo etil adicional no P3EHT causa um completo rearranjo das moléculas e dificulta seu empacotamento. Constatou-se ainda pouca variação das curvas de DIPSHIFT para os carbonos da cadeia lateral como função do método de excitação utilizado, o que aponta para um polímero que apresenta cadeia lateral móvel mesmo em sua fase cristalina. Os dados de dinâmica molecular foram corroborados por medidas de T1, T1ρ e TCH. Utilizando filtros dipolares em baixo campo observou-se três temperaturas de transição para o P3EHT: 250 K, 325 K e 350 K. A cristalização desse material é um processo lento. Verificou-se que o mesmo pode se estender por até até 24h a temperatura ambiente. Mudanças no espectro de 13C utilizando CPMAS em alto campo indicam um ordenamento dos anéis tiofeno (empacotamento π – π) como o principal processo de cristalização para o P3EHT.

Polarized interacting exciton gas in quantum wells and bulk semiconductors

We develop a theory to calculate exciton binding energies of both two- and three-dimensional spin polarized exciton gases within a mean field approach. Our method allows the analysis of recent experiments showing the importance of the polarization and intensity of the excitation light on the exciton luminescence of GaAs quantum wells. We study the breaking of the spin degeneracy observed at high exciton density (5×1010 cm2). Energy level splitting between spin +1 and spin -1 is shown to be due to many-body interexcitonic exchange while the spin relaxation time is controlled by intraexciton exchange. © 1996 The American Physical Society.

Spin splitting in a polarized quasi-two-dimensional exciton gas

We have observed a large spin splitting between "spin" +1 and -1 heavy-hole excitons, having unbalanced populations, in undoped GaAs/AlAs quantum wells in the absence of any external magnetic field. Time-resolved photoluminescence spectroscopy, under excitation with circularly polarized light, reveals that, for high excitonic density and short times after the pulsed excitation, the emission from majority excitons lies above that of minority ones. The amount of the splitting, which can be as large as 50% of the binding energy, increases with excitonic density and presents a time evolution closely connected with the degree of polarization of the luminescence. Our results are interpreted on the light of a recently developed model, which shows that, while intraexcitonic exchange interaction is responsible for the spin relaxation processes, exciton-exciton interaction produces a breaking of the spin degeneracy in two-dimensional semiconductors.

Exact and analytic-numerical solutions of lagging models of heat transfer in a semi-infinite medium

Different non-Fourier models of heat conduction have been considered in recent years, in a growing area of applications, to model microscale and ultrafast, transient, nonequilibrium responses in heat and mass transfer. In this work, using Fourier transforms, we obtain exact solutions for different lagging models of heat conduction in a semi-infinite domain, which allow the construction of analytic-numerical solutions with prescribed accuracy. Examples of numerical computations, comparing the properties of the models considered, are presented.