Upconversion of infrared-to-visible light in Pr3+-Yb3+ codoped fluoroindate glass

Bright fluorescence in the visible range has been observed in Pr3+-Yb3+ doped fluoroindate glass under infrared diode laser irradiation. The mechanism which contributes for the upconversion emission is identified and the energy transfer rate between Pr3+-Yb3+ is obtained for different concentrations. © 1998 Elsevier Science B.V. All rights reserved.

Structural refinement, growth mechanism, infrared/Raman spectroscopies and photoluminescence properties of PbMoO4 crystals

Lead molybdate (PbMoO4) crystals were synthesized by the co-precipitation method at room temperature and then processed in a conventional hydrothermal (CH) system at low temperature (70 °C for different times). These crystals were structurally characterized by X-ray diffraction (XRD), Rietveld refinement, micro-Raman (MR) and Fourier transformed infrared (FT-IR) spectroscopies. Field emission scanning electron microscopy images were employed to observe the shape and monitor the crystal growth process. The optical properties were investigated by ultraviolet-visible (UV-Vis) absorption and photoluminescence (PL) measurements. XRD patterns and MR spectra indicate that these crystals have a scheelite-type tetragonal structure. Rietveld refinement data possibilities the evaluation of distortions in the tetrahedral [MoO 4] clusters. MR and FT-IR spectra exhibited a high mode ν1(Ag) ascribed to symmetric stretching vibrations as well as a large absorption band with two modes ν3(Eu and Au) related to anti-symmetric stretching vibrations in [MoO 4] clusters. Growth mechanisms were proposed to explain the stages involved for the formation of octahedron-like PbMoO4 crystals. UV-Vis absorption spectra indicate a reduction in optical band gap with an increase in the CH processing time. PL properties of PbMoO4 crystals have been elucidated using a model based on distortions of tetrahedral [MoO4] clusters due to medium-range intrinsic defects and intermediary energy levels (deep and shallow holes) within the band gap. © 2012 Elsevier Ltd. All rights reserved.

Near-infrared nonlinearity of a multicomponent tellurium oxide glass at 800 and 1,064 nm

We report on the nonlinear (NL) optical properties of glassy TeO2-GeO2-K2O-Bi2O3 at lambda = 800 nm and lambda = 1,064 nm. Using the Kerr gate technique with a laser delivering 150 fs pulses at 800 nm, we demonstrated the fast NL response of the samples. The modulus of the NL refractive index, n (2), at 800 nm was similar to 10(-15) cm(2)/W. The Z-scan technique was used to determine n (2) a parts per thousand +10(-15) cm(2)/W, at 1,064 nm with pulses of 17 ps. The two-photon absorption coefficient, alpha (2), was smaller than the minimum that we can measure (< 0.003 cm/GW). The figure of merit n (2)/alpha (2) lambda was calculated and indicates that this glass composition has large potential to be used for all-optical switching.

Infrared to visible up-conversion in biocellulose yttrium vanadate nanoparticle composite membranes. Demonstration of chloroaluminum phthalocyanine light emission under up-converted light excitation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Mid-infrared supercontinuum generation in a suspended-core As2S3 chalcogenide microstructured optical fiber

We demonstrate the supercontinuum (SC) generation in a suspended-core As2S3 chalcogenide microstructured optical fiber (MOF). The variation of SC is investigated by changing the fiber length, pump peak power and pump wavelength. In the case of long fibers (20 and 40 cm), the SC ranges are discontinuous and stop at the wavelengths shorter than 3500 nm, due to the absorption of fiber. In the case of short fibers (1.3 and 2.4 cm), the SC ranges are continuous and can extend to the wavelengths longer than 4 μm. The SC broadening is observed when the pump peak power increases from 0.24 to 1.32 kW at 2500 nm. The SC range increases with the pump wavelength changing from 2200 to 2600 nm, corresponding to the dispersion of As2S3 MOF from the normal to anomalous region. The SC generation is simulated by the generalized nonlinear Schrödinger equation. The simulation includes the SC difference between 1.3 and 2.4 cm long fiber by 2500 nm pumping, the variation of SC with pump peak power in 2.4 cm long fiber, and the variation of SC with pump wavelength in 1.3 cm long fiber. The simulation agrees well with the experiment.

Multioctave infrared supercontinuum generation in large-core As2S3 fibers

We report on infrared supercontinuum (SC) generation through laser filamentation and subsequent nonlinear propagation in a step-index As2S3 fiber. The 100 μm core and high-purity As2S3 fiber used exhibit zero-dispersion wavelength around 4.5 μm, a mid-infrared background loss of 0.2dB/m, and a maximum loss of only 0.55dB/m at the S-H absorption peak around 4.05 μm. When pumping with ultrashort laser pulses slightly above the S-H absorption band, broadband infrared supercontinua were generated with a 20 dB spectral flatness spanning from 1.5 up to 7 μm. The efficiency and spectral shape of the SC produced by ultrashort pulses in large-core As2S3 fiber are mainly determined by its dispersion, the S-H contaminant absorption, and the mid-infrared nonlinear absorption.

Enhancement of optical absorption by modulation of the oxygen flow of TiO2 films deposited by reactive sputtering

Oxygen-deficient TiO2 films with enhanced visible and near-infrared optical absorption have been deposited by reactive sputtering using a planar diode radio frequency magnetron configuration. It is observed that the increase in the absorption coefficient is more effective when the O-2 gas supply is periodically interrupted rather than by a decrease of the partial O-2 gas pressure in the deposition plasma. The optical absorption coefficient at 1.5 eV increases from about 1 x 10(2) cm(-1) to more than 4 x 10(3) cm(-1) as a result of the gas flow discontinuity. A red-shift of similar to 0.24 eV in the optical absorption edge is also observed. High resolution transmission electron microscopy with composition analysis shows that the films present a dense columnar morphology, with estimated mean column width of 40nm. Moreover, the interruptions of the O-2 gas flow do not produce detectable variations in the film composition along its growing direction. X-ray diffraction and micro-Raman experiments indicate the presence of the TiO2 anatase, rutile, and brookite phases. The anatase phase is dominant, with a slight increment of the rutile and brookite phases in films deposited under discontinued O-2 gas flow. The increase of optical absorption in the visible and near-infrared regions has been attributed to a high density of defects in the TiO2 films, which is consistent with density functional theory calculations that place oxygen-related vacancy states in the upper third of the optical bandgap. The electronic structure calculation results, along with the adopted deposition method and experimental data, have been used to propose a mechanism to explain the formation of the observed oxygen-related defects in TiO2 thin films. The observed increase in sub-bandgap absorption and the modeling of the corresponding changes in the electronic structure are potentially useful concerning the optimization of efficiency of the photocatalytic activity and the magnetic doping of TiO2 films. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4724334]

Retrieval of trace gases vertical profile in the lower atmosphere combining. Differential Optical Absorption Spectroscopy with radiative transfer models

The motivation for the work presented in this thesis is to retrieve profile information for the atmospheric trace constituents nitrogen dioxide (NO2) and ozone (O3) in the lower troposphere from remote sensing measurements. The remote sensing technique used, referred to as Multiple AXis Differential Optical Absorption Spectroscopy (MAX-DOAS), is a recent technique that represents a significant advance on the well-established DOAS, especially for what it concerns the study of tropospheric trace consituents. NO2 is an important trace gas in the lower troposphere due to the fact that it is involved in the production of tropospheric ozone; ozone and nitrogen dioxide are key factors in determining the quality of air with consequences, for example, on human health and the growth of vegetation. To understand the NO2 and ozone chemistry in more detail not only the concentrations at ground but also the acquisition of the vertical distribution is necessary. In fact, the budget of nitrogen oxides and ozone in the atmosphere is determined both by local emissions and non-local chemical and dynamical processes (i.e. diffusion and transport at various scales) that greatly impact on their vertical and temporal distribution: thus a tool to resolve the vertical profile information is really important. Useful measurement techniques for atmospheric trace species should fulfill at least two main requirements. First, they must be sufficiently sensitive to detect the species under consideration at their ambient concentration levels. Second, they must be specific, which means that the results of the measurement of a particular species must be neither positively nor negatively influenced by any other trace species simultaneously present in the probed volume of air. Air monitoring by spectroscopic techniques has proven to be a very useful tool to fulfill these desirable requirements as well as a number of other important properties. During the last decades, many such instruments have been developed which are based on the absorption properties of the constituents in various regions of the electromagnetic spectrum, ranging from the far infrared to the ultraviolet. Among them, Differential Optical Absorption Spectroscopy (DOAS) has played an important role. DOAS is an established remote sensing technique for atmospheric trace gases probing, which identifies and quantifies the trace gases in the atmosphere taking advantage of their molecular absorption structures in the near UV and visible wavelengths of the electromagnetic spectrum (from 0.25 μm to 0.75 μm). Passive DOAS, in particular, can detect the presence of a trace gas in terms of its integrated concentration over the atmospheric path from the sun to the receiver (the so called slant column density). The receiver can be located at ground, as well as on board an aircraft or a satellite platform. Passive DOAS has, therefore, a flexible measurement configuration that allows multiple applications. The ability to properly interpret passive DOAS measurements of atmospheric constituents depends crucially on how well the optical path of light collected by the system is understood. This is because the final product of DOAS is the concentration of a particular species integrated along the path that radiation covers in the atmosphere. This path is not known a priori and can only be evaluated by Radiative Transfer Models (RTMs). These models are used to calculate the so called vertical column density of a given trace gas, which is obtained by dividing the measured slant column density to the so called air mass factor, which is used to quantify the enhancement of the light path length within the absorber layers. In the case of the standard DOAS set-up, in which radiation is collected along the vertical direction (zenith-sky DOAS), calculations of the air mass factor have been made using “simple” single scattering radiative transfer models. This configuration has its highest sensitivity in the stratosphere, in particular during twilight. This is the result of the large enhancement in stratospheric light path at dawn and dusk combined with a relatively short tropospheric path. In order to increase the sensitivity of the instrument towards tropospheric signals, measurements with the telescope pointing the horizon (offaxis DOAS) have to be performed. In this circumstances, the light path in the lower layers can become very long and necessitate the use of radiative transfer models including multiple scattering, the full treatment of atmospheric sphericity and refraction. In this thesis, a recent development in the well-established DOAS technique is described, referred to as Multiple AXis Differential Optical Absorption Spectroscopy (MAX-DOAS). The MAX-DOAS consists in the simultaneous use of several off-axis directions near the horizon: using this configuration, not only the sensitivity to tropospheric trace gases is greatly improved, but vertical profile information can also be retrieved by combining the simultaneous off-axis measurements with sophisticated RTM calculations and inversion techniques. In particular there is a need for a RTM which is capable of dealing with all the processes intervening along the light path, supporting all DOAS geometries used, and treating multiple scattering events with varying phase functions involved. To achieve these multiple goals a statistical approach based on the Monte Carlo technique should be used. A Monte Carlo RTM generates an ensemble of random photon paths between the light source and the detector, and uses these paths to reconstruct a remote sensing measurement. Within the present study, the Monte Carlo radiative transfer model PROMSAR (PROcessing of Multi-Scattered Atmospheric Radiation) has been developed and used to correctly interpret the slant column densities obtained from MAX-DOAS measurements. In order to derive the vertical concentration profile of a trace gas from its slant column measurement, the AMF is only one part in the quantitative retrieval process. One indispensable requirement is a robust approach to invert the measurements and obtain the unknown concentrations, the air mass factors being known. For this purpose, in the present thesis, we have used the Chahine relaxation method. Ground-based Multiple AXis DOAS, combined with appropriate radiative transfer models and inversion techniques, is a promising tool for atmospheric studies in the lower troposphere and boundary layer, including the retrieval of profile information with a good degree of vertical resolution. This thesis has presented an application of this powerful comprehensive tool for the study of a preserved natural Mediterranean area (the Castel Porziano Estate, located 20 km South-West of Rome) where pollution is transported from remote sources. Application of this tool in densely populated or industrial areas is beginning to look particularly fruitful and represents an important subject for future studies.

Origin and Nature of Radio-Loud Broad Absorption Line Quasars

The origin of Broad Absorption Line Quasars (BAL QSOs) is still an open issue. Accounting for ~20% of the QSO population, these objects present broad absorption lines in their optical spectra generated from outflows with velocities up to 0.2 c. Nowadays, the hypotheses about their nature are principally related to orientation or evolutionary scenarios. In the first one, absorption lines are produced by outflows originated by the accretion disk, basically present in all QSOs, but seen only when they intercept the line of sight. In the second hypothesis, BAL QSOs would be young or recently re-fueled QSOs, still ejecting their dust cocoon. In this case orientation would not play a role, since the absorption features would be produced by spherically ejected matter. In this work we present the results of a multi-frequency study of a Radio-Loud BAL QSO sample, and a comparison sample of Radio-Loud non-BAL QSOs. We performed observations from radio to Near-Infrared, aiming at collecting useful informations about the orientation, the age, and the morphologies of these objects. Various techniques have been applied, including local and continental radio interferometry, single dish observations and spectroscopy. The comparison with the non-BAL QSO sample allows us to conclude that no particular orientation is present in BAL QSOs. Moreover, various morphologies and ages can be found, analogously to "normal" QSOs. Thus, the solution to this astrophysical problem seems not to reside in a peculiarity of the BAL QSO subclass with respect to non-BAL QSOs, since both the studied models do not completely explain the observed characteristics. Further experiments with future instrumentation will allow us to underline useful differences and test the physical conditions in BAL QSOs.

Study of molecules of astrochemical, astrophysical and atmospheric interest by means of High - Resolution Infrared Spectroscopy

The spectroscopic investigation of the gas-phase molecules relevant for the chemistry of the atmosphere and of the interstellar medium has been performed. Two types of molecules have been studied, linear and symmetric top. Several experimental high-resolution techniques have been adopted, exploiting the spectrometers available in Bologna, Venezia, Brussels and Wuppertal: Fourier-Transform-Infrared Spectroscopy, Cavity-Ring-Down Spectroscopy, Cavity-Enhanced-Absorption Spectroscopy, Tunable-Diode-Laser Spectroscopy. Concerning linear molecules, the spectra of a number of isotopologues of acetylene, 12C2D2, H12C13CD, H13C12CD, 13C12CD2, of DCCF and monodeuterodiacetylene DC4H, have been studied, from 320 to 6800 cm-1. This interval covers bending, stretching, overtone and combination bands, the focus on specific ranges depending on the molecule. In particular, the analysis of the bending modes has been performed for 12C2D2 (450-2200 cm-1), 13C12CD2 (450-1700 cm-1), DCCF (320-850cm-1) and DC4H (450-1100 cm-1), of the stretching-bending system for 12C2D2 (450-5500 cm-1) and of the 2nu1 and combination bands up to four quanta of excitation for H12C13CD, H13C12CD and 13C12CD2 (6130-6800 cm-1). In case of symmetric top molecules, CH3CCH has been investigated in the 2nu1 region (6200-6700 cm-1), which is particularly congested due to the huge network of states affected by Coriolis and anharmonic interactions. The bending fundamentals of 15ND3 (450-2700 cm-1) have been studied for the first time, characterizing completely the bending states, v2 = 1 and v4 = 1, whereas the analysis of the stretching modes, which evidenced the presence of several perturbations, has been started. Finally, the fundamental band nu4 of CF3Br in the 1190-1220 cm-1 region has been investigated. Transitions belonging to the CF379Br and CF381Br molecules have been identified since the spectra were recorded using a sample containing the two isotopologues in natural abundance. This allowed the characterization of the v4 = 1 state for both isotopologues and the evaluation of the bromine isotopic splitting.

Ferrocene-terminated alkanethiol self-assembled monolayers: An electrochemical and in situ surface-enhanced infra-red absorption spectroscopy study

The effect of anions on the redox behavior and structure of 11-ferrocenyl-1-undecanethiol (FcC11) monolayers (SAM) on Au(1 1 1) single crystal and Au(1 1 1-25 nm) thin film electrodes was investigated in 0.1 M solutions of HPF6, HClO4, HBF4, HNO3, and H2SO4 by cyclic voltammetry (CV) and in situ surface-enhanced infrared reflection-absorption spectroscopy (SEIRAS). We demonstrate that the FcC11 redox peaks shift toward positive potentials and broaden with increasing hydrophilicity of the anions. In situ surface-enhanced IR-spectroscopy (SEIRAS) provided direct access for the incorporation of anions into the oxidized adlayer. The coadsorption of anions is accompanied by the penetration of water molecules. The latter effect is particularly pronounced in aqueous HNO3 and H2SO4 electrolytes. The adlayer permeability increases with increasing hydrophilicity of the anions. We also found that even the neutral (reduced) FcC11 SAM is permeable for water molecules. Based on the property of interfacial water to reorient upon charge inversion, we propose a spectroscopic approach for estimating the potential of zero total charge of the FcC11-modified Au(1 1 1) electrodes in aqueous electrolytes.

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.

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.

Non-destructive optical characterization of fruits in the red and near infrared.

Increasing attention is being paid to the possible development of non-invasive tests for the assessment of the quality of Fruits. We propose a novel non-destructive method for the measurement of the internal optical properties of fruits and vegetables by means of lime-resolved reflectance spectroscopy in the visible and NIR range. A Fully automated instrumentation for time-resolved reflectance measurements was developed. It is based on mode-locked laser sources and electronics for time-correlated single photon counting, and provides a time-resolution of 120-160 ps. The system was used to probe the optical properties of several species and varieties of Fruits and vegetables in the red and NIR range (650-1000 nm). In most Fruits, the absorption line shape is dominated by the absorption peak of water, centred around 970 nm. Generally, the absorption spectra also show the spectral features typical of chlorophyll, with maximum at 675 nm. In particular, for what concerns apples, variations in peak intensity are observed depending on the variety, the degree of ripeness as well as the position on the apple. For all the species and varieties considered, the transport scattering coefficient decreases progressively upon increasing the wavelength.