O 1s excitation and ionization processes in the CO2 molecule studied via detection of low-energy fluorescence emission

Oxygen 1s excitation and ionization processes in the CO2 molecule have been studied with dispersed and non-dispersed fluorescence spectroscopy as well as with the vacuum ultraviolet (VUV) photon?photoion coincidence technique. The intensity of the neutral O emission line at 845 nm shows particular sensitivity to core-to-Rydberg excitations and core?valence double excitations, while shape resonances are suppressed. In contrast, the partial fluorescence yield in the wavelength window 300?650 nm and the excitation functions of selected O+ and C+ emission lines in the wavelength range 400?500 nm display all of the absorption features. The relative intensity of ionic emission in the visible range increases towards higher photon energies, which is attributed to O 1s shake-off photoionization. VUV photon?photoion coincidence spectra reveal major contributions from the C+ and O+ ions and a minor contribution from C2+. No conclusive changes in the intensity ratios among the different ions are observed above the O 1s threshold. The line shape of the VUV?O+ coincidence peak in the mass spectrum carries some information on the initial core excitation

Research on intermediate band solar cells and development of experimental techniques for their characterization under concentrated illumination

Abstract This work is a contribution to the research and development of the intermediate band solar cell (IBSC), a high efficiency photovoltaic concept that features the advantages of both low and high bandgap solar cells. The resemblance with a low bandgap solar cell comes from the fact that the IBSC hosts an electronic energy band -the intermediate band (IB)- within the semiconductor bandgap. This IB allows the collection of sub-bandgap energy photons by means of two-step photon absorption processes, from the valence band (VB) to the IB and from there to the conduction band (CB). The exploitation of these low energy photons implies a more efficient use of the solar spectrum. The resemblance of the IBSC with a high bandgap solar cell is related to the preservation of the voltage: the open-circuit voltage (VOC) of an IBSC is not limited by any of the sub-bandgaps (involving the IB), but only by the fundamental bandgap (defined from the VB to the CB). Nevertheless, the presence of the IB allows new paths for electronic recombination and the performance of the IBSC is degraded at 1 sun operation conditions. A theoretical argument is presented regarding the need for the use of concentrated illumination in order to circumvent the degradation of the voltage derived from the increase in the recombi¬nation. This theory is supported by the experimental verification carried out with our novel characterization technique consisting of the acquisition of photogenerated current (IL)-VOC pairs under low temperature and concentrated light. Besides, at this stage of the IBSC research, several new IB materials are being engineered and our novel character¬ization tool can be very useful to provide feedback on their capability to perform as real IBSCs, verifying or disregarding the fulfillment of the “voltage preservation” principle. An analytical model has also been developed to assess the potential of quantum-dot (QD)-IBSCs. It is based on the calculation of band alignment of III-V alloyed heterojunc-tions, the estimation of the confined energy levels in a QD and the calculation of the de¬tailed balance efficiency. Several potentially useful QD materials have been identified, such as InAs/AlxGa1-xAs, InAs/GaxIn1-xP, InAs1-yNy/AlAsxSb1-x or InAs1-zNz/Alx[GayIn1-y]1-xP. Finally, a model for the analysis of the series resistance of a concentrator solar cell has also been developed to design and fabricate IBSCs adapted to 1,000 suns. Resumen Este trabajo contribuye a la investigación y al desarrollo de la célula solar de banda intermedia (IBSC), un concepto fotovoltaico de alta eficiencia que auna las ventajas de una célula solar de bajo y de alto gap. La IBSC se parece a una célula solar de bajo gap (o banda prohibida) en que la IBSC alberga una banda de energía -la banda intermedia (IB)-en el seno de la banda prohibida. Esta IB permite colectar fotones de energía inferior a la banda prohibida por medio de procesos de absorción de fotones en dos pasos, de la banda de valencia (VB) a la IB y de allí a la banda de conducción (CB). El aprovechamiento de estos fotones de baja energía conlleva un empleo más eficiente del espectro solar. La semejanza antre la IBSC y una célula solar de alto gap está relacionada con la preservación del voltaje: la tensión de circuito abierto (Vbc) de una IBSC no está limitada por ninguna de las fracciones en las que la IB divide a la banda prohibida, sino que está únicamente limitada por el ancho de banda fundamental del semiconductor (definido entre VB y CB). No obstante, la presencia de la IB posibilita nuevos caminos de recombinación electrónica, lo cual degrada el rendimiento de la IBSC a 1 sol. Este trabajo argumenta de forma teórica la necesidad de emplear luz concentrada para evitar compensar el aumento de la recom¬binación de la IBSC y evitar la degradación del voltage. Lo anterior se ha verificado experimentalmente por medio de nuestra novedosa técnica de caracterización consistente en la adquisicin de pares de corriente fotogenerada (IL)-VOG en concentración y a baja temperatura. En esta etapa de la investigación, se están desarrollando nuevos materiales de IB y nuestra herramienta de caracterizacin está siendo empleada para realimentar el proceso de fabricación, comprobando si los materiales tienen capacidad para operar como verdaderas IBSCs por medio de la verificación del principio de preservación del voltaje. También se ha desarrollado un modelo analítico para evaluar el potencial de IBSCs de puntos cuánticos. Dicho modelo está basado en el cálculo del alineamiento de bandas de energía en heterouniones de aleaciones de materiales III-V, en la estimación de la energía de los niveles confinados en un QD y en el cálculo de la eficiencia de balance detallado. Este modelo ha permitido identificar varios materiales de QDs potencialmente útiles como InAs/AlxGai_xAs, InAs/GaxIni_xP, InAsi_yNy/AlAsxSbi_x ó InAsi_zNz/Alx[GayIni_y]i_xP. Finalmente, también se ha desarrollado un modelado teórico para el análisis de la resistencia serie de una célula solar de concentración. Gracias a dicho modelo se han diseñado y fabricado IBSCs adaptadas a 1.000 soles.

Deep levels in a-plane, high Mg-content MgxZn1-xO epitaxial layers grown by molecular beam epitaxy

Deep level defects in n-type unintentionally doped a-plane MgxZn1−xO, grown by molecular beam epitaxy on r-plane sapphire were fully characterized using deep level optical spectroscopy (DLOS) and related methods. Four compositions of MgxZn1−xO were examined with x = 0.31, 0.44, 0.52, and 0.56 together with a control ZnO sample. DLOS measurements revealed the presence of five deep levels in each Mg-containing sample, having energy levels of Ec − 1.4 eV, 2.1 eV, 2.6 V, and Ev + 0.3 eV and 0.6 eV. For all Mg compositions, the activation energies of the first three states were constant with respect to the conduction band edge, whereas the latter two revealed constant activation energies with respect to the valence band edge. In contrast to the ternary materials, only three levels, at Ec − 2.1 eV, Ev + 0.3 eV, and 0.6 eV, were observed for the ZnO control sample in this systematically grown series of samples. Substantially higher concentrations of the deep levels at Ev + 0.3 eV and Ec − 2.1 eV were observed in ZnO compared to the Mg alloyed samples. Moreover, there is a general invariance of trap concentration of the Ev + 0.3 eV and 0.6 eV levels on Mg content, while at least and order of magnitude dependency of the Ec − 1.4 eV and Ec − 2.6 eV levels in Mg alloyed samples.

Absorption coefficient for the intraband transitions in quantum dot materials

In this paper, we present calculations of the absorption coefficient for transitions between the bound states of quantum dots grown within a semiconductor and the extended states of the conduction band. For completeness, transitions among bound states are also presented. In the separation of variables, single band k·p model is used in which most elements may be expressed analytically. The analytical formulae are collected in the appendix of this paper. It is concluded that the transitions are strong enough to provide a quick path to the conduction band for electrons pumped from the valence to the intermediate band

Understanding intermediate-band solar cells

The intermediate-band solar cell is designed to provide a large photogenerated current while maintaining a high output voltage. To make this possible, these cells incorporate an energy band that is partially filled with electrons within the forbidden bandgap of a semiconductor. Photons with insufficient energy to pump electrons from the valence band to the conduction band can use this intermediate band as a stepping stone to generate an electron-hole pair. Nanostructured materials and certain alloys have been employed in the practical implementation of intermediate-band solar cells, although challenges still remain for realizing practical devices. Here we offer our present understanding of intermediate-band solar cells, as well as a review of the different approaches pursed for their practical implementation. We also discuss how best to resolve the remaining technical issues.

Analysis of the modified optical properties and band structure of GaAs12xSbx-capped InAs/GaAs quantum dots

The origin of the modified optical properties of InAs/GaAs quantum dots (QD) capped with a thin GaAs1−xSbx layer is analyzed in terms of the band structure. To do so, the size, shape, and composition of the QDs and capping layer are determined through cross-sectional scanning tunnelling microscopy and used as input parameters in an 8 × 8 k·p model. As the Sb content is increased, there are two competing effects determining carrier confinement and the oscillator strength: the increased QD height and reduced strain on one side and the reduced QD-capping layer valence band offset on the other. Nevertheless, the observed evolution of the photoluminescence (PL) intensity with Sb cannot be explained in terms of the oscillator strength between ground states, which decreases dramatically for Sb > 16%, where the band alignment becomes type II with the hole wavefunction localized outside the QD in the capping layer. Contrary to this behaviour, the PL intensity in the type II QDs is similar (at 15 K) or even larger (at room temperature) than in the type I Sb-free reference QDs. This indicates that the PL efficiency is dominated by carrier dynamics, which is altered by the presence of the GaAsSb capping layer. In particular, the presence of Sb leads to an enhanced PL thermal stability. From the comparison between the activation energies for thermal quenching of the PL and the modelled band structure, the main carrier escape mechanisms are suggested. In standard GaAs-capped QDs, escape of both electrons and holes to the GaAs barrier is the main PL quenching mechanism. For small-moderate Sb (<16%) for which the type I band alignment is kept, electrons escape to the GaAs barrier and holes escape to the GaAsSb capping layer, where redistribution and retraping processes can take place. For Sb contents above 16% (type-II region), holes remain in the GaAsSb layer and the escape of electrons from the QD to the GaAs barrier is most likely the dominant PL quenching mechanism. This means that electrons and holes behave dynamically as uncorrelated pairs in both the type-I and type-II structures.

Experimental determination of the eutectic temperature in air of the CuO-TiO2 pseudobinary system

Eutectic temperature and composition in the CuO–TiO2 pseudobinary system have been experimentally determined in air by means differential thermal analysis (DTA), thermogravimetry (TG) and hot-stage microscopy (HSM). Samples of the new eutectic composition treated at different temperatures have been characterized by X-ray diffraction (XRD) and X-ray absorption near-edge structural spectroscopy (XANES) to identify phases and to determine the Cu valence state, respectively. The results show that the eutectic temperature in air is higher by 100 °C (∼1000 °C) for a Ti-richer composition (XTiO2=25 mol%) than the one calculated in the literature. The reduction of Cu2+ to Cu+ takes places at about 1030 °C. The existence of Cu2TiO3 and Cu3TiO4 has been confirmed by XRD in the temperature range between 1045 and 1200 °C.

Vanadium-Doped In and Sn Sulphides: Photocatalysts able to use the whole visible light spectrum

Using photocatalysis for energy applications depends, more than for environmental purposes or selective chemical synthesis, on converting as much of the solar spectrum as possible; the best photocatalyst, titania, is far from this. Many efforts are pursued to use better that spectrum in photocatalysis, by doping titania or using other materials (mainly oxides, nitrides and sulphides) to obtain a lower bandgap, even if this means decreasing the chemical potential of the electron-hole pairs. Here we introduce an alternative scheme, using an idea recently proposed for photovoltaics: the intermediate band (IB) materials. It consists in introducing in the gap of a semiconductor an intermediate level which, acting like a stepstone, allows an electron jumping from the valence band to the conduction band in two steps, each one absorbing one sub-bandgap photon. For this the IB must be partially filled, to allow both sub-bandgap transitions to proceed at comparable rates; must be made of delocalized states to minimize nonradiative recombination; and should not communicate electronically with the outer world. For photovoltaic use the optimum efficiency so achievable, over 1.5 times that given by a normal semiconductor, is obtained with an overall bandgap around 2.0 eV (which would be near-optimal also for water phtosplitting). Note that this scheme differs from the doping principle usually considered in photocatalysis, which just tries to decrease the bandgap; its aim is to keep the full bandgap chemical potential but using also lower energy photons. In the past we have proposed several IB materials based on extensively doping known semiconductors with light transition metals, checking first of all with quantum calculations that the desired IB structure results. Subsequently we have synthesized in powder form two of them: the thiospinel In2S3 and the layered compound SnS2 (having bandgaps of 2.0 and 2.2 eV respectively) where the octahedral cation is substituted at a â?10% level with vanadium, and we have verified that this substitution introduces in the absorption spectrum the sub-bandgap features predicted by the calculations. With these materials we have verified, using a simple reaction (formic acid oxidation), that the photocatalytic spectral response is indeed extended to longer wavelengths, being able to use even 700 nm photons, without largely degrading the response for above-bandgap photons (i.e. strong recombination is not induced) [3b, 4]. These materials are thus promising for efficient photoevolution of hydrogen from water; work on this is being pursued, the results of which will be presented.

New Intermediate band sulphide nanoparticles acting in the full visible light range spectra as an active photocatalyst

Nowadays one of the challenges of materials science is to find new technologies that will be able to make the most of renewable energies. An example of new proposals in this field are the intermediate-band (IB) materials, which promise higher efficiencies in photovoltaic applications (through the intermediate band solar cells), or in heterogeneous photocatalysis (using nanoparticles of them, for the light-induced degradation of pollutants or for the efficient photoevolution of hydrogen from water). An IB material consists in a semiconductor in which gap a new level is introduced [1], the intermediate band (IB), which should be partially filled by electrons and completely separated of the valence band (VB) and of the conduction band (CB). This scheme (figure 1) allows an electron from the VB to be promoted to the IB, and from the latter to the CB, upon absorption of photons with energy below the band gap Eg, so that energy can be absorbed in a wider range of the solar spectrum and a higher current can be obtained without sacrificing the photovoltage (or the chemical driving force) corresponding to the full bandgap Eg, thus increasing the overall efficiency. This concept, applied to photocatalysis, would allow using photons of a wider visible range while keeping the same redox capacity. It is important to note that this concept differs from the classic photocatalyst doping principle, which essentially tries just to decrease the bandgap. This new type of materials would keep the full bandgap potential but would use also lower energy photons. In our group several IB materials have been proposed, mainly for the photovoltaic application, based on extensively doping known semiconductors with transition metals [2], examining with DFT calculations their electronic structures. Here we refer to In2S3 and SnS2, which contain octahedral cations; when doped with Ti or V an IB is formed according to quantum calculations (see e.g. figure 2). We have used a solvotermal synthesis method to prepare in nanocrystalline form the In2S3 thiospinel and the layered compound SnS2 (which when undoped have bandgaps of 2.0 and 2.2 eV respectively) where the cation is substituted by vanadium at a ?10% level. This substitution has been studied, characterizing the materials by different physical and chemical techniques (TXRF, XRD, HR-TEM/EDS) (see e.g. figure 3) and verifying with UV spectrometry that this substitution introduces in the spectrum the sub-bandgap features predicted by the calculations (figure 4). For both sulphide type nanoparticles (doped and undoped) the photocatalytic activity was studied by following at room temperature the oxidation of formic acid in aqueous suspension, a simple reaction which is easily monitored by UV-Vis spectroscopy. The spectral response of the process is measured using a collection of band pass filters that allow only some wavelengths into the reaction system. Thanks to this method the spectral range in which the materials are active in the photodecomposition (which coincides with the band gap for the undoped samples) can be checked, proving that for the vanadium substituted samples this range is increased, making possible to cover all the visible light range. Furthermore it is checked that these new materials are more photocorrosion resistant than the toxic CdS witch is a well know compound frequently used in tests of visible light photocatalysis. These materials are thus promising not only for degradation of pollutants (or for photovoltaic cells) but also for efficient photoevolution of hydrogen from water; work in this direction is now being pursued.

Intermediate Band to Conduction Band optical absorption in ZnTe:O

ZnTe doped with high concentrations of oxygen has been proposed in previous works as intermediate band (IB) material for photovoltaic applications. The existence of extra optical transitions related to the presence of an IB has already been demonstrated in this material and it has been possible to measure the absorption coefficient of the transitions from the valence band (VB) to the IB. In this work we present the first measurement of the absorption coefficient associated to transitions from the IB to the conduction band (CB) in ZnTe:O. The samples used are 4 ?m thick ZnTe layers with or without O in a concentration ~ 1019 cm-3, which have been grown on semi-insulating GaAs substrates by molecular beam epitaxy (MBE). The IB-CB absorption coefficient peaks for photon energies ~ 0.4 eV. It is extracted from reflectance and transmittance spectra measured using Fourier Transform Infrared (FTIR) spectroscopy. Under typical FTIR measurement conditions (low light intensity, broadband spectrum) the absorption coefficient in IB-to-CB transitions reaches 700 cm-1. This is much weaker than the one observed for VB-IB absorption. This result is consistent with the fact that the IB is expected to be nearly empty of electrons under equilibrium conditions in ZnTe(:O). The absorption for VB to IB transitions is also observed in the same samples through reflectance measurements performed in the visible range using a monochromator. These measurements are compared with the quantum efficiency (QE) from solar cells fabricated under similar conditions.

A numerical study into the influence of quantum dot size on the sub-bandgap interband photocurrent in intermediate band solar cells

A numerical study is presented of the sub-bandgap interband photon absorption in quantum dot intermediate band solar cells. Absorption coefficients and photocurrent densities are calculated for the valence band to intermediate band transitions using a four-band k · p method. It is found that reducing the quantum dot width in the plane perpendicular to the growth direction increases the photocurrent from the valence band to the intermediate-band ground state if the fractional surface coverage of quantum dots is conserved. This provides a path to increase the sub-bandgap photocurrent in intermediate band solar cells.

Photon Management Structures for Absorption Enhancement in Intermediate Band Solar Cells and Crystalline Silicon Solar Cells

El objetivo de la tesis es investigar los beneficios que el atrapamiento de la luz mediante fenómenos difractivos puede suponer para las células solares de silicio cristalino y las de banda intermedia. Ambos tipos de células adolecen de una insuficiente absorción de fotones en alguna región del espectro solar. Las células solares de banda intermedia son teóricamente capaces de alcanzar eficiencias mucho mayores que los dispositivos convencionales (con una sola banda energética prohibida), pero los prototipos actuales se resienten de una absorción muy débil de los fotones con energías menores que la banda prohibida. Del mismo modo, las células solares de silicio cristalino absorben débilmente en el infrarrojo cercano debido al carácter indirecto de su banda prohibida. Se ha prestado mucha atención a este problema durante las últimas décadas, de modo que todas las células solares de silicio cristalino comerciales incorporan alguna forma de atrapamiento de luz. Por razones de economía, en la industria se persigue el uso de obleas cada vez más delgadas, con lo que el atrapamiento de la luz adquiere más importancia. Por tanto aumenta el interés en las estructuras difractivas, ya que podrían suponer una mejora sobre el estado del arte. Se comienza desarrollando un método de cálculo con el que simular células solares equipadas con redes de difracción. En este método, la red de difracción se analiza en el ámbito de la óptica física, mediante análisis riguroso con ondas acopladas (rigorous coupled wave analysis), y el sustrato de la célula solar, ópticamente grueso, se analiza en los términos de la óptica geométrica. El método se ha implementado en ordenador y se ha visto que es eficiente y da resultados en buen acuerdo con métodos diferentes descritos por otros autores. Utilizando el formalismo matricial así derivado, se calcula el límite teórico superior para el aumento de la absorción en células solares mediante el uso de redes de difracción. Este límite se compara con el llamado límite lambertiano del atrapamiento de la luz y con el límite absoluto en sustratos gruesos. Se encuentra que las redes biperiódicas (con geometría hexagonal o rectangular) pueden producir un atrapamiento mucho mejor que las redes uniperiódicas. El límite superior depende mucho del periodo de la red. Para periodos grandes, las redes son en teoría capaces de alcanzar el máximo atrapamiento, pero sólo si las eficiencias de difracción tienen una forma peculiar que parece inalcanzable con las herramientas actuales de diseño. Para periodos similares a la longitud de onda de la luz incidente, las redes de difracción pueden proporcionar atrapamiento por debajo del máximo teórico pero por encima del límite Lambertiano, sin imponer requisitos irrealizables a la forma de las eficiencias de difracción y en un margen de longitudes de onda razonablemente amplio. El método de cálculo desarrollado se usa también para diseñar y optimizar redes de difracción para el atrapamiento de la luz en células solares. La red propuesta consiste en un red hexagonal de pozos cilíndricos excavados en la cara posterior del sustrato absorbente de la célula solar. La red se encapsula en una capa dieléctrica y se cubre con un espejo posterior. Se simula esta estructura para una célula solar de silicio y para una de banda intermedia y puntos cuánticos. Numéricamente, se determinan los valores óptimos del periodo de la red y de la profundidad y las dimensiones laterales de los pozos para ambos tipos de células. Los valores se explican utilizando conceptos físicos sencillos, lo que nos permite extraer conclusiones generales que se pueden aplicar a células de otras tecnologías. Las texturas con redes de difracción se fabrican en sustratos de silicio cristalino mediante litografía por nanoimpresión y ataque con iones reactivos. De los cálculos precedentes, se conoce el periodo óptimo de la red que se toma como una constante de diseño. Los sustratos se procesan para obtener estructuras precursoras de células solares sobre las que se realizan medidas ópticas. Las medidas de reflexión en función de la longitud de onda confirman que las redes cuadradas biperiódicas consiguen mejor atrapamiento que las uniperiódicas. Las estructuras fabricadas se simulan con la herramienta de cálculo descrita en los párrafos precedentes y se obtiene un buen acuerdo entre la medida y los resultados de la simulación. Ésta revela que una fracción significativa de los fotones incidentes son absorbidos en el reflector posterior de aluminio, y por tanto desaprovechados, y que este efecto empeora por la rugosidad del espejo. Se desarrolla un método alternativo para crear la capa dieléctrica que consigue que el reflector se deposite sobre una superficie plana, encontrándose que en las muestras preparadas de esta manera la absorción parásita en el espejo es menor. La siguiente tarea descrita en la tesis es el estudio de la absorción de fotones en puntos cuánticos semiconductores. Con la aproximación de masa efectiva, se calculan los niveles de energía de los estados confinados en puntos cuánticos de InAs/GaAs. Se emplea un método de una y de cuatro bandas para el cálculo de la función de onda de electrones y huecos, respectivamente; en el último caso se utiliza un hamiltoniano empírico. La regla de oro de Fermi permite obtener la intensidad de las transiciones ópticas entre los estados confinados. Se investiga el efecto de las dimensiones del punto cuántico en los niveles de energía y la intensidad de las transiciones y se obtiene que, al disminuir la anchura del punto cuántico respecto a su valor en los prototipos actuales, se puede conseguir una transición más intensa entre el nivel intermedio fundamental y la banda de conducción. Tomando como datos de partida los niveles de energía y las intensidades de las transiciones calculados como se ha explicado, se desarrolla un modelo de equilibrio o balance detallado realista para células solares de puntos cuánticos. Con el modelo se calculan las diferentes corrientes debidas a transiciones ópticas entre los numerosos niveles intermedios y las bandas de conducción y de valencia bajo ciertas condiciones. Se distingue de modelos de equilibrio detallado previos, usados para calcular límites de eficiencia, en que se adoptan suposiciones realistas sobre la absorción de fotones para cada transición. Con este modelo se reproducen datos publicados de eficiencias cuánticas experimentales a diferentes temperaturas con un acuerdo muy bueno. Se muestra que el conocido fenómeno del escape térmico de los puntos cuánticos es de naturaleza fotónica; se debe a los fotones térmicos, que inducen transiciones entre los estados excitados que se encuentran escalonados en energía entre el estado intermedio fundamental y la banda de conducción. En el capítulo final, este modelo realista de equilibrio detallado se combina con el método de simulación de redes de difracción para predecir el efecto que tendría incorporar una red de difracción en una célula solar de banda intermedia y puntos cuánticos. Se ha de optimizar cuidadosamente el periodo de la red para equilibrar el aumento de las diferentes transiciones intermedias, que tienen lugar en serie. Debido a que la absorción en los puntos cuánticos es extremadamente débil, se deduce que el atrapamiento de la luz, por sí solo, no es suficiente para conseguir corrientes apreciables a partir de fotones con energía menor que la banda prohibida en las células con puntos cuánticos. Se requiere una combinación del atrapamiento de la luz con un incremento de la densidad de puntos cuánticos. En el límite radiativo y sin atrapamiento de la luz, se necesitaría que el número de puntos cuánticos de una célula solar se multiplicara por 1000 para superar la eficiencia de una célula de referencia con una sola banda prohibida. En cambio, una célula con red de difracción precisaría un incremento del número de puntos en un factor 10 a 100, dependiendo del nivel de la absorción parásita en el reflector posterior. Abstract The purpose of this thesis is to investigate the benefits that diffractive light trapping can offer to quantum dot intermediate band solar cells and crystalline silicon solar cells. Both solar cell technologies suffer from incomplete photon absorption in some part of the solar spectrum. Quantum dot intermediate band solar cells are theoretically capable of achieving much higher efficiencies than conventional single-gap devices. Present prototypes suffer from extremely weak absorption of subbandgap photons in the quantum dots. This problem has received little attention so far, yet it is a serious barrier to the technology approaching its theoretical efficiency limit. Crystalline silicon solar cells absorb weakly in the near infrared due to their indirect bandgap. This problem has received much attention over recent decades, and all commercial crystalline silicon solar cells employ some form of light trapping. With the industry moving toward thinner and thinner wafers, light trapping is becoming of greater importance and diffractive structures may offer an improvement over the state-of-the-art. We begin by constructing a computational method with which to simulate solar cells equipped with diffraction grating textures. The method employs a wave-optical treatment of the diffraction grating, via rigorous coupled wave analysis, with a geometric-optical treatment of the thick solar cell bulk. These are combined using a steady-state matrix formalism. The method has been implemented computationally, and is found to be efficient and to give results in good agreement with alternative methods from other authors. The theoretical upper limit to absorption enhancement in solar cells using diffractions gratings is calculated using the matrix formalism derived in the previous task. This limit is compared to the so-called Lambertian limit for light trapping with isotropic scatterers, and to the absolute upper limit to light trapping in bulk absorbers. It is found that bi-periodic gratings (square or hexagonal geometry) are capable of offering much better light trapping than uni-periodic line gratings. The upper limit depends strongly on the grating period. For large periods, diffraction gratings are theoretically able to offer light trapping at the absolute upper limit, but only if the scattering efficiencies have a particular form, which is deemed to be beyond present design capabilities. For periods similar to the incident wavelength, diffraction gratings can offer light trapping below the absolute limit but above the Lambertian limit without placing unrealistic demands on the exact form of the scattering efficiencies. This is possible for a reasonably broad wavelength range. The computational method is used to design and optimise diffraction gratings for light trapping in solar cells. The proposed diffraction grating consists of a hexagonal lattice of cylindrical wells etched into the rear of the bulk solar cell absorber. This is encapsulated in a dielectric buffer layer, and capped with a rear reflector. Simulations are made of this grating profile applied to a crystalline silicon solar cell and to a quantum dot intermediate band solar cell. The grating period, well depth, and lateral well dimensions are optimised numerically for both solar cell types. This yields the optimum parameters to be used in fabrication of grating equipped solar cells. The optimum parameters are explained using simple physical concepts, allowing us to make more general statements that can be applied to other solar cell technologies. Diffraction grating textures are fabricated on crystalline silicon substrates using nano-imprint lithography and reactive ion etching. The optimum grating period from the previous task has been used as a design parameter. The substrates have been processed into solar cell precursors for optical measurements. Reflection spectroscopy measurements confirm that bi-periodic square gratings offer better absorption enhancement than uni-periodic line gratings. The fabricated structures have been simulated with the previously developed computation tool, with good agreement between measurement and simulation results. The simulations reveal that a significant amount of the incident photons are absorbed parasitically in the rear reflector, and that this is exacerbated by the non-planarity of the rear reflector. An alternative method of depositing the dielectric buffer layer was developed, which leaves a planar surface onto which the reflector is deposited. It was found that samples prepared in this way suffered less from parasitic reflector absorption. The next task described in the thesis is the study of photon absorption in semiconductor quantum dots. The bound-state energy levels of in InAs/GaAs quantum dots is calculated using the effective mass approximation. A one- and four- band method is applied to the calculation of electron and hole wavefunctions respectively, with an empirical Hamiltonian being employed in the latter case. The strength of optical transitions between the bound states is calculated using the Fermi golden rule. The effect of the quantum dot dimensions on the energy levels and transition strengths is investigated. It is found that a strong direct transition between the ground intermediate state and the conduction band can be promoted by decreasing the quantum dot width from its value in present prototypes. This has the added benefit of reducing the ladder of excited states between the ground state and the conduction band, which may help to reduce thermal escape of electrons from quantum dots: an undesirable phenomenon from the point of view of the open circuit voltage of an intermediate band solar cell. A realistic detailed balance model is developed for quantum dot solar cells, which uses as input the energy levels and transition strengths calculated in the previous task. The model calculates the transition currents between the many intermediate levels and the valence and conduction bands under a given set of conditions. It is distinct from previous idealised detailed balance models, which are used to calculate limiting efficiencies, since it makes realistic assumptions about photon absorption by each transition. The model is used to reproduce published experimental quantum efficiency results at different temperatures, with quite good agreement. The much-studied phenomenon of thermal escape from quantum dots is found to be photonic; it is due to thermal photons, which induce transitions between the ladder of excited states between the ground intermediate state and the conduction band. In the final chapter, the realistic detailed balance model is combined with the diffraction grating simulation method to predict the effect of incorporating a diffraction grating into a quantum dot intermediate band solar cell. Careful optimisation of the grating period is made to balance the enhancement given to the different intermediate transitions, which occur in series. Due to the extremely weak absorption in the quantum dots, it is found that light trapping alone is not sufficient to achieve high subbandgap currents in quantum dot solar cells. Instead, a combination of light trapping and increased quantum dot density is required. Within the radiative limit, a quantum dot solar cell with no light trapping requires a 1000 fold increase in the number of quantum dots to supersede the efficiency of a single-gap reference cell. A quantum dot solar cell equipped with a diffraction grating requires between a 10 and 100 fold increase in the number of quantum dots, depending on the level of parasitic absorption in the rear reflector.

On the production of N-2(+) ions at the N 1s edge of the nitrogen molecule

The N+2 ion yield of the N2 molecule has been measured at the N 1s → Rydberg excitations. It displays Fano-type line shapes due to interference between direct outer-valence photoionization and participator decay of the core-excited Rydberg states. The N+2 ion yield is compared with the total intensity of the outer-valence photoelectron lines obtained recently with electron spectroscopy (Kivimäki et al 2012 Phys. Rev. A 86 012516). The increasing difference between the two curves at the higher core-to-Rydberg excitations is most likely due to soft x-ray emission processes that are followed by autoionization. The results also suggest that resonant Auger decay from the core–valence doubly excited states contributes to the N+2 ion yield at the photon energies that are located on both sides of the N 1s ionization limit.

Interband absorption of photons by extended states in intermediate band solar cells

This paper considers sub-bandgap photon absorption in an InAs/GaAs quantum dot matrix. Absorption coefficients are calculated for transitions from the extended states in the valence band to confined states in the conduction band. This completes a previous body of work in which transitions between bound states were calculated. The calculations are based on the empirical k·p Hamiltonian considering the quantum dots as parallelepipeds. The extended states may be only partially extended?in one or two dimensions?or extended in all three dimensions. It is found that extended-to-bound transitions are, in general, weaker than bound-to-bound transitions, and that the former are weaker when the initial state is extended in more coordinates. This study is of direct application to the research of intermediate band solar cells and other semiconductor devices based on light absorption in semiconductors nanostructured with quantum dots.

User Experience in Human-Technology Interaction. Communication, context and evaluation methodology

En esta Tesis se presentan dos líneas de investigación relacionadas y que contribuyen a las áreas de Interacción Hombre-Tecnología (o Máquina; siglas en inglés: HTI o HMI), lingüística computacional y evaluación de la experiencia del usuario. Las dos líneas en cuestión son el diseño y la evaluación centrada en el usuario de sistemas de Interacción Hombre-Máquina avanzados. En la primera parte de la Tesis (Capítulos 2 a 4) se abordan cuestiones fundamentales del diseño de sistemas HMI avanzados. El Capítulo 2 presenta una panorámica del estado del arte de la investigación en el ámbito de los sistemas conversacionales multimodales, con la que se enmarca el trabajo de investigación presentado en el resto de la Tesis. Los Capítulos 3 y 4 se centran en dos grandes aspectos del diseño de sistemas HMI: un gestor del diálogo generalizado para tratar la Interacción Hombre-Máquina multimodal y sensible al contexto, y el uso de agentes animados personificados (ECAs) para mejorar la robustez del diálogo, respectivamente. El Capítulo 3, sobre gestión del diálogo, aborda el tratamiento de la heterogeneidad de la información proveniente de las modalidades comunicativas y de los sensores externos. En este capítulo se propone, en un nivel de abstracción alto, una arquitectura para la gestión del diálogo con influjos heterogéneos de información, apoyándose en el uso de State Chart XML. En el Capítulo 4 se presenta una contribución a la representación interna de intenciones comunicativas, y su traducción a secuencias de gestos a ejecutar por parte de un ECA, diseñados específicamente para mejorar la robustez en situaciones de diálogo críticas que pueden surgir, por ejemplo, cuando se producen errores de entendimiento en la comunicación entre el usuario humano y la máquina. Se propone, en estas páginas, una extensión del Functional Mark-up Language definido en el marco conceptual SAIBA. Esta extensión permite representar actos comunicativos que realizan intenciones del emisor (la máquina) que no se pretende sean captadas conscientemente por el receptor (el usuario humano), pero con las que se pretende influirle a éste e influir el curso del diálogo. Esto se consigue mediante un objeto llamado Base de Intenciones Comunicativas (en inglés, Communication Intention Base, o CIB). La representación en el CIB de intenciones “no claradas” además de las explícitas permite la construcción de actos comunicativos que realizan simultáneamente varias intenciones comunicativas. En el Capítulo 4 también se describe un sistema experimental para el control remoto (simulado) de un asistente domótico, con autenticación de locutor para dar acceso, y con un ECA en el interfaz de cada una de estas tareas. Se incluye una descripción de las secuencias de comportamiento verbal y no verbal de los ECAs, que fueron diseñados específicamente para determinadas situaciones con objeto de mejorar la robustez del diálogo. Los Capítulos 5 a 7 conforman la parte de la Tesis dedicada a la evaluación. El Capítulo 5 repasa antecedentes relevantes en la literatura de tecnologías de la información en general, y de sistemas de interacción hablada en particular. Los principales antecedentes en el ámbito de la evaluación de la interacción sobre los cuales se ha desarrollado el trabajo presentado en esta Tesis son el Technology Acceptance Model (TAM), la herramienta Subjective Assessment of Speech System Interfaces (SASSI), y la Recomendación P.851 de la ITU-T. En el Capítulo 6 se describen un marco y una metodología de evaluación aplicados a la experiencia del usuario con sistemas HMI multimodales. Se desarrolló con este propósito un novedoso marco de evaluación subjetiva de la calidad de la experiencia del usuario y su relación con la aceptación por parte del mismo de la tecnología HMI (el nombre dado en inglés a este marco es Subjective Quality Evaluation Framework). En este marco se articula una estructura de clases de factores subjetivos relacionados con la satisfacción y aceptación por parte del usuario de la tecnología HMI propuesta. Esta estructura, tal y como se propone en la presente tesis, tiene dos dimensiones ortogonales. Primero se identifican tres grandes clases de parámetros relacionados con la aceptación por parte del usuario: “agradabilidad ” (likeability: aquellos que tienen que ver con la experiencia de uso, sin entrar en valoraciones de utilidad), rechazo (los cuales sólo pueden tener una valencia negativa) y percepción de utilidad. En segundo lugar, este conjunto clases se reproduce para distintos “niveles, o focos, percepción del usuario”. Éstos incluyen, como mínimo, un nivel de valoración global del sistema, niveles correspondientes a las tareas a realizar y objetivos a alcanzar, y un nivel de interfaz (en los casos propuestos en esta tesis, el interfaz es un sistema de diálogo con o sin un ECA). En el Capítulo 7 se presenta una evaluación empírica del sistema descrito en el Capítulo 4. El estudio se apoya en los mencionados antecedentes en la literatura, ampliados con parámetros para el estudio específico de los agentes animados (los ECAs), la auto-evaluación de las emociones de los usuarios, así como determinados factores de rechazo (concretamente, la preocupación por la privacidad y la seguridad). También se evalúa el marco de evaluación subjetiva de la calidad propuesto en el capítulo anterior. Los análisis de factores efectuados revelan una estructura de parámetros muy cercana conceptualmente a la división de clases en utilidad-agradabilidad-rechazo propuesta en dicho marco, resultado que da cierta validez empírica al marco. Análisis basados en regresiones lineales revelan estructuras de dependencias e interrelación entre los parámetros subjetivos y objetivos considerados. El efecto central de mediación, descrito en el Technology Acceptance Model, de la utilidad percibida sobre la relación de dependencia entre la intención de uso y la facilidad de uso percibida, se confirma en el estudio presentado en la presente Tesis. Además, se ha encontrado que esta estructura de relaciones se fortalece, en el estudio concreto presentado en estas páginas, si las variables consideradas se generalizan para cubrir más ampliamente las categorías de agradabilidad y utilidad contempladas en el marco de evaluación subjetiva de calidad. Se ha observado, asimismo, que los factores de rechazo aparecen como un componente propio en los análisis de factores, y además se distinguen por su comportamiento: moderan la relación entre la intención de uso (que es el principal indicador de la aceptación del usuario) y su predictor más fuerte, la utilidad percibida. Se presentan también resultados de menor importancia referentes a los efectos de los ECAs sobre los interfaces de los sistemas de diálogo y sobre los parámetros de percepción y las valoraciones de los usuarios que juegan un papel en conformar su aceptación de la tecnología. A pesar de que se observa un rendimiento de la interacción dialogada ligeramente mejor con ECAs, las opiniones subjetivas son muy similares entre los dos grupos experimentales (uno interactuando con un sistema de diálogo con ECA, y el otro sin ECA). Entre las pequeñas diferencias encontradas entre los dos grupos destacan las siguientes: en el grupo experimental sin ECA (es decir, con interfaz sólo de voz) se observó un efecto más directo de los problemas de diálogo (por ejemplo, errores de reconocimiento) sobre la percepción de robustez, mientras que el grupo con ECA tuvo una respuesta emocional más positiva cuando se producían problemas. Los ECAs parecen generar inicialmente expectativas más elevadas en cuanto a las capacidades del sistema, y los usuarios de este grupo se declaran más seguros de sí mismos en su interacción. Por último, se observan algunos indicios de efectos sociales de los ECAs: la “amigabilidad ” percibida los ECAs estaba correlada con un incremento la preocupación por la seguridad. Asimismo, los usuarios del sistema con ECAs tendían más a culparse a sí mismos, en lugar de culpar al sistema, de los problemas de diálogo que pudieran surgir, mientras que se observó una ligera tendencia opuesta en el caso de los usuarios del sistema con interacción sólo de voz. ABSTRACT This Thesis presents two related lines of research work contributing to the general fields of Human-Technology (or Machine) Interaction (HTI, or HMI), computational linguistics, and user experience evaluation. These two lines are the design and user-focused evaluation of advanced Human-Machine (or Technology) Interaction systems. The first part of the Thesis (Chapters 2 to 4) is centred on advanced HMI system design. Chapter 2 provides a background overview of the state of research in multimodal conversational systems. This sets the stage for the research work presented in the rest of the Thesis. Chapers 3 and 4 focus on two major aspects of HMI design in detail: a generalised dialogue manager for context-aware multimodal HMI, and embodied conversational agents (ECAs, or animated agents) to improve dialogue robustness, respectively. Chapter 3, on dialogue management, deals with how to handle information heterogeneity, both from the communication modalities or from external sensors. A highly abstracted architectural contribution based on State Chart XML is proposed. Chapter 4 presents a contribution for the internal representation of communication intentions and their translation into gestural sequences for an ECA, especially designed to improve robustness in critical dialogue situations such as when miscommunication occurs. We propose an extension of the functionality of Functional Mark-up Language, as envisaged in much of the work in the SAIBA framework. Our extension allows the representation of communication acts that carry intentions that are not for the interlocutor to know of, but which are made to influence him or her as well as the flow of the dialogue itself. This is achieved through a design element we have called the Communication Intention Base. Such r pr s ntation of “non- clar ” int ntions allows th construction of communication acts that carry several communication intentions simultaneously. Also in Chapter 4, an experimental system is described which allows (simulated) remote control to a home automation assistant, with biometric (speaker) authentication to grant access, featuring embodied conversation agents for each of the tasks. The discussion includes a description of the behavioural sequences for the ECAs, which were designed for specific dialogue situations with particular attention given to the objective of improving dialogue robustness. Chapters 5 to 7 form the evaluation part of the Thesis. Chapter 5 reviews evaluation approaches in the literature for information technologies, as well as in particular for speech-based interaction systems, that are useful precedents to the contributions of the present Thesis. The main evaluation precedents on which the work in this Thesis has built are the Technology Acceptance Model (TAM), the Subjective Assessment of Speech System Interfaces (SASSI) tool, and ITU-T Recommendation P.851. Chapter 6 presents the author’s work in establishing an valuation framework and methodology applied to the users’ experience with multimodal HMI systems. A novel user-acceptance Subjective Quality Evaluation Framework was developed by the author specifically for this purpose. A class structure arises from two orthogonal sets of dimensions. First we identify three broad classes of parameters related with user acceptance: likeability factors (those that have to do with the experience of using the system), rejection factors (which can only have a negative valence) and perception of usefulness. Secondly, the class structure is further broken down into several “user perception levels”; at the very least: an overall system-assessment level, task and goal-related levels, and an interface level (e.g., a dialogue system with or without an ECA). An empirical evaluation of the system described in Chapter 4 is presented in Chapter 7. The study was based on the abovementioned precedents in the literature, expanded with categories covering the inclusion of an ECA, the users’ s lf-assessed emotions, and particular rejection factors (privacy and security concerns). The Subjective Quality Evaluation Framework proposed in the previous chapter was also scrutinised. Factor analyses revealed an item structure very much related conceptually to the usefulness-likeability-rejection class division introduced above, thus giving it some empirical weight. Regression-based analysis revealed structures of dependencies, paths of interrelations, between the subjective and objective parameters considered. The central mediation effect, in the Technology Acceptance Model, of perceived usefulness on the dependency relationship of intention-to-use with perceived ease of use was confirmed in this study. Furthermore, the pattern of relationships was stronger for variables covering more broadly the likeability and usefulness categories in the Subjective Quality Evaluation Framework. Rejection factors were found to have a distinct presence as components in factor analyses, as well as distinct behaviour: they were found to moderate the relationship between intention-to-use (the main measure of user acceptance) and its strongest predictor, perceived usefulness. Insights of secondary importance are also given regarding the effect of ECAs on the interface of spoken dialogue systems and the dimensions of user perception and judgement attitude that may have a role in determining user acceptance of the technology. Despite observing slightly better performance values in the case of the system with the ECA, subjective opinions regarding both systems were, overall, very similar. Minor differences between two experimental groups (one interacting with an ECA, the other only through speech) include a more direct effect of dialogue problems (e.g., non-understandings) on perceived dialogue robustness for the voice-only interface test group, and a more positive emotional response for the ECA test group. Our findings further suggest that the ECA generates higher initial expectations, and users seem slightly more confident in their interaction with the ECA than do those without it. Finally, mild evidence of social effects of ECAs was also found: the perceived friendliness of the ECA increased security concerns, and ECA users may tend to blame themselves rather than the system when dialogue problems are encountered, while the opposite may be true for voice-only users.