Spectroscopic study of lanthanide squarate hydrates

In the present investigation some spectroscopic properties of several lanthanide squarate hydrates are reported. The Raman spectra show the same distinctive Jahn-Teller intensity pattern for non-totally symmetric modes, as previously observed for the free anion. In the case of the terbium salt, the Tb3+ emission is very intense even at room temperature, revealing an efficient excitation via the ligand electronic levels. The Tb3+ dilution in Gd3+ or La3+ hosts increases this excitation efficiency without any appreciable variation in the 5D4 excited-state lifetime. However, the Eu3+ emission is very weak, with excited states located above the 5D2 level (ca. 21 550 cm-1) being completely quenched at room temperature. At lower temperatures higher-lying levels are not so efficiently quenched. The broad band observed in the UV excitation spectra of Eu3+ and Tb3+ is easily assigned to an intra-ligand transition leading to ligand-to-lanthanide ion energy transfer processes. As observed for Tb3+, Eu3+ dilution in Gd3+ or La3+ hosts also increases the relative emission intensity mediated by the ligand, without variation in the 5D0 excited-state lifetime. The Eu3+ 5D0 excitation spectra show vibronic structures that can be interpreted on the basis of the data available from the vibrational spectra. An increase in the vibronic intensities is observed as the lanthanide concentration is increased. © 1994.

Visible to infrared energy conversion in Pr3+-Yb3+ co-doped fluoroindate glasses

Processes involving visible to infrared energy conversion are presented for Pr3+-Yb3+ co-doped fluoroindate glasses. The emission in the visible and infrared regions, the luminescence decay time of the Pr 3+:3P0 → 3H4 (482 nm), Pr3+:1D2 → 3H6 (800 nm), Yb3+:2F5/2 → 2F 7/2 (1044 nm) transitions and the photoluminescence excitation spectra were measured in Pr3+ samples and in Pr3+-Yb 3+ samples as a function of the Yb3+ concentration. In addition, energy transfer efficiencies were estimated from Pr3+: 3P0 and Pr3+:1D2 levels to Yb3+:2F7/2 level. Down-Conversion (DC) emission is observed due to a combination of two different processes: 1-a one-step cross relaxation (Pr3+:3P0 → 1G4; Yb3+:2F7/2 → 2F5/2) resulting in one photon emitted by Pr3+ (1G4 → 3H5) and one photon emitted by Yb3+ (2F7/2 → 2F5/2); 2-a resonant two-step first order energy transfer, where the first part of energy is transferred to Yb3+ neighbor through cross relaxation (Pr3+:3P0 → 1G4; Yb3+:2F7/2 → 2F5/2) followed by a second energy transfer step (Pr 3+:1G4 → 3H4; Yb3+:2F7/2 → 2F5/2). A third process leading to one IR photon emission to each visible photon absorbed involves cross relaxation energy transfer (Pr3+: 1D2 → 3F4; Yb 3+:2F7/2 → 2F5/2). © 2013 Elsevier B.V. All rights reserved.

Complexos de európio e /ou de zinco com ácido 3-piridinocarboxílico

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Estudo dos difenilfosfinatos de lantânio ativados por cério, európio e térbio emissores luminescentes multicores

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

End-to-end Distance Distribution in Fluorescent Derivatives of Bradykinin in Interaction with Lipid Vesicles

Cellular membranes have relevant roles in processes related to proteases like human kallikreins and cathepsins. As enzyme and substrate may interact with cell membranes and associated co-factors, it is important to take into account the behavior of peptide substrates in the lipid environment. In this paper we report an study based on energy transfer in two bradykinin derived peptides labeled with the donor-acceptor pair Abz/Eddnp (ortho-aminobenzoic acid/N-[2,4-dinitrophenyl]-ethylenediamine). Time-resolved fluorescence experiments were performed in phosphate buffer and in the presence of large unilamelar vesicles of phospholipids, and of micelles of sodium dodecyl sulphate (SDS). The decay kinetics were analyzed using the program CONTIN to obtain end-to-end distance distribution functions f(r). Despite of the large difference in the number of residues the end-to-end distance of the longer peptide (9 amino acid residues) is only 20 % larger than the values obtained for the shorter peptide (5 amino acid residues). The proline residue, in position 4 of the bradykinin sequence promotes a turn in the longer peptide chain, shortening its end-to-end distance. The surfactant SDS has a strong disorganizing effect, substantially broadening the distance distributions, while temperature increase has mild effects in the flexibility of the chains, causing small increase in the distribution width. The interaction with phospholipid vesicles stabilizes more compact conformations, decreasing end-to-end distances in the peptides. Anisotropy experiments showed that rotational diffusion was not severely affected by the interaction with the vesicles, suggesting a location for the peptides in the surface region of the bilayer, a result consistent with small effect of lipid phase transition on the peptides conformations.

A MODIS-Based Energy Balance to Estimate Evapotranspiration for Clear-Sky Days in Brazilian Tropical Savannas

Evapotranspiration (ET) plays an important role in global climate dynamics and in primary production of terrestrial ecosystems; it represents the mass and energy transfer from the land to atmosphere. Limitations to measuring ET at large scales using ground-based methods have motivated the development of satellite remote sensing techniques. The purpose of this work is to evaluate the accuracy of the SEBAL algorithm for estimating surface turbulent heat fluxes at regional scale, using 28 images from MODIS. SEBAL estimates are compared with eddy-covariance (EC) measurements and results from the hydrological model MGB-IPH. SEBAL instantaneous estimates of latent heat flux (LE) yielded r(2) = 0.64 and r(2) = 0.62 over sugarcane croplands and savannas when compared against in situ EC estimates. At the same sites, daily aggregated estimates of LE were r(2) = 0.76 and r(2) = 0.66, respectively. Energy balance closure showed that turbulent fluxes over sugarcane croplands were underestimated by 7% and 9% over savannas. Average daily ET from SEBAL is in close agreement with estimates from the hydrological model for an overlay of 38,100 km(2) (r(2) = 0.88). Inputs to which the algorithm is most sensitive are vegetation index (NDVI), gradient of temperature (dT) to compute sensible heat flux (H) and net radiation (Re). It was verified that SEBAL has a tendency to overestimate results both at local and regional scales probably because of low sensitivity to soil moisture and water stress. Nevertheless the results confirm the potential of the SEBAL algorithm, when used with MODIS images for estimating instantaneous LE and daily ET from large areas.

Atmospheric radiative transfer in multiple scattering conditions. Application to NWP models.

High spectral resolution radiative transfer (RT) codes are essential tools in the study of the radiative energy transfer in the Earth atmosphere and a support for the development of parameterizations for fast RT codes used in climate and weather prediction models. Cirrus clouds cover permanently 30% of the Earth's surface, representing an important contribution to the Earth-atmosphere radiation balance. The work has been focussed on the development of the RT model LBLMS. The model, widely tested in the infra-red spectral range, has been extended to the short wave spectrum and it has been used in comparison with airborne and satellite measurements to study the optical properties of cirrus clouds. A new database of single scattering properties has been developed for mid latitude cirrus clouds. Ice clouds are treated as a mixture of ice crystals with various habits. The optical properties of the mixture are tested in comparison to radiometric measurements in selected case studies. Finally, a parameterization of the mixture for application to weather prediction and global circulation models has been developed. The bulk optical properties of ice crystals are parameterized as functions of the effective dimension of measured particle size distributions that are representative of mid latitude cirrus clouds. Tests with the Limited Area Weather Prediction model COSMO have shown the impact of the new parameterization with respect to cirrus cloud optical properties based on ice spheres.

Einzelmolekülspektroskopische Untersuchung von Rylenfarbstoffen zur elektronischen Wechselwirkung in multichromophoren Systemen und zur thermischen Besetzung molekularer Schwingungszustände

Im ersten Teil der Arbeit wurde die Abstandsabhängigkeit des elektronischen Kopplungsverhaltens für eine homologe Reihe von Perylendiimid-Dimeren (PDI-(Ph)x-PDI, x=0-3) mithilfe der Einzelmolekülspektroskopie bei tiefen Temperaturen untersucht. Während für große Abstände überwiegend „schwache“ Kopplung dominierte, wurde für den kleinsten Abstand „starke“ Kopplung gefunden. Im Gegensatz dazu zeigte das p-Phenylen-verbrückte Dimer (x=1) in Abhängigkeit vom untersuchten Molekül ein für beide Grenzfälle typisches Verhalten. Hier entscheidet die Größe der Kopplungsstärke im Vergleich zum statischen Energieunterschied, welcher Kopplungsmechanismus vorliegt. Die homologe Reihe ermöglichte zusätzlich die quantitative Untersuchung der Abstandsabhängigkeit der elektronischen Kopplungsstärke im Grenzfall „schwacher“ Kopplung. Sie konnte direkt aus der zugrunde liegenden Energietransferdynamik ermittelt werden. Der Vergleich mit quantenchemisch berechneten Werten lieferte eine gute Übereinstimmung. Die Abweichung betrug lediglich 20%.rnIm zweiten Teil der Arbeit wurde die thermische Besetzung der Schwingungszustände einzelner Terrylen-Moleküle untersucht. Im elektronischen Grundzustand konnte sie mithilfe von anti-Stokes-Fluoreszenz infolge von „Hot Band“ Absorption nachgewiesen werden. Darüber hinaus wurde Fluoreszenz aus höheren Schwingungszuständen des elektronisch angeregten Zustandes gefunden, die auf „Hot Band“ Emission infolge von thermischer Besetzung zurückgeführt werden konnte. Durch die Kombination von Emissions- und Anregungsspektroskopie konnte die Temperaturabhängigkeit beider Prozesse im Temperaturbereich von 209-311 K untersucht werden. Sie folgt der Boltzmann-Statistik, was eine Temperaturmessung mit einzelnen Molekülen ermöglicht. rn

Factors improving the vibration transfer of the floating mass transducer at the round window

With the placement of a floating mass transducer (FMT) at the round window, a new approach of coupling an implantable hearing system to the cochlea has been introduced. The aim of the present experimental study is to examine the influence of different ways of FMT placement at the round window on the vibration energy transfer to the cochlea.

Conformational transitions of glycine induced by vibrational excitation of the O-H stretch

Vibrational energy flow and conformational transitions following excitation of the OH stretching mode of the most stable conformer of glycine are studied by classical trajectories. "On the fly" simulations with the PM3 semiempirical electronic structure method for the potential surface are used. Initial conditions are selected to correspond to the v = 1 excitation of the OH stretch. The main findings are: (1) An an equilibrium-like ratio is established between the populations of the 3 lowest-lying conformers after about 10 picoseconds. (2) There is a high probability throughout the 150 ps of the simulations for finding the molecule in geometries far from the equilibrium structures of the lowest-energy conformers. (3) Energy from the initial excited OH (v = 1) stretch flows preferentially to 5 other vibrational modes, including the bending motion of the H atom. (4) RRK theory yields conformational transition rates that deviate substantially from the classical trajectory results. Possible implication of these results for vibrational energy flow and conformational transitions in small biological molecules are discussed.

Enhanced (1)G(4) emission in NaLaF4: Pr3+, Yb3+ and charge transfer in NaLaF4: Ce3+, Yb3+ studied by fourier transform luminescence spectroscopy

A high resolution luminescence study of NaLaF4: 1%Pr3+, 5%Yb3+ and NaLaF4: 1%Ce3+, 5%Yb3+ in the UV to NIR spectral range using a InGaAs detector and a fourier transform interferometer is reported. Although the Pr3+(P-3(0) -> (1)G(4), Yb3+(F-2(7/2) -> F-2(5/2)) energy transfer step takes place, significant Pr3+ (1)G(4) emission around 993, 1330 and 1850 nm is observed. No experimental proof for the second energy transfer step in the down-conversion process between Pr3+ and Yb3+ can be given. In the case of NaLaF4: Ce3+, Yb3+ it is concluded that the observed Yb3+ emission upon Ce3+ 5d excitation is the result of a charge transfer process instead of down-conversion. (C) 2010 Elsevier B.V. All rights reserved.

Gas-phase Lifetimes of Nucleobase Analogues by Picosecond Pumpionization and Streak Techniques

The picosecond (ps) timescale is relevant for the investigation of many molecular dynamical processes such as fluorescence, nonradiative relaxation, intramolecular vibrational relaxation, molecular rotation and intermolecular energy transfer, to name a few. While investigations of ultrafast (femtosecond) processes of biological molecules, e.g. nucleobases and their analogues in the gas phase are available, there are few investigations on the ps time scale. We have constructed a ps pump-ionization setup and a ps streak camera fluorescence apparatus for the determination of lifetimes of supersonic jet-cooled and isolated molecules and clusters. The ps pump-ionization setup was used to determine the lifetimes of the nucleobase analogue 2-aminopurine (2AP) and of two 2AP˙(H2O)n water cluster isomers with n=1 and 2. Their lifetimes lie between 150 ps and 3 ns and are strongly cluster-size dependent. The ps streak camera setup was used to determine accurate fluorescence lifetimes of the uracil analogue 2-pyridone (2PY), its self-dimer (2PY)2, two isomers of its trimer (2PY)3 and its tetramer (2PY)4, which lie in the 7–12 ns range.

Spectroscopic and functional investigations of the AMPA subtype of ionotropic glutamate receptors

Ion channels play a crucial role in the functioning of different systems of the body because of their ability to bridge the cell membrane and allow ions to pass in and out of the cell. Ionotropic glutamate receptors are one class of these important proteins and have been shown to be critical in propagating synaptic transmission in the central nervous system and in other diverse functions throughout the body. Because of their wide-ranging effects, this family of receptors is an important target for structure-function investigations to understand their mechanism of action. ^ α-Amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid (AMPA) receptors are one subtype of glutamate receptors and have been shown to be the primary receptors involved in rapid excitatory signaling in the central nervous system. Agonist binding to the extracellular ligand binding domain of these receptors causes various conformational changes that culminate in formation of the ion channel. Previous structural investigations have provided important information about their mechanism of action, including uncovering a relationship between the degree of cleft closure in the binding domain and activation of the receptor. However, what question remains unanswered is how specific interactions between the agonist and the protein interplay with cleft closure to mediate receptor activation. ^ To investigate this question, I applied a multiscale approach to investigate the effects of agonist binding on various levels. Vibrational spectroscopy was utilized to investigate molecular-level interactions in the binding pocket, and fluorescence resonance energy transfer (FRET) was employed to measure cleft closure in the isolated ligand binding domain. The results of these studies in the isolated binding domain were then correlated to activation of the full receptor. These investigations showed a relationship between the strength of the interaction at the α-amine group of the agonist and extent of receptor activation, where a stronger interaction correlated to a larger activation, which was upheld even when the extent of cleft closure did not correlate to activation. These results show that this interaction at the α-amine group is critical in mediating the allosteric mechanism of activation and provide a bit more insight into how agonist binding is coupled to channel gating in AMPA receptors. ^

Advances in the Simultaneous Multiple Surface optical design method for imaging and non-imaging applications

Classical imaging optics has been developed over centuries in many areas, such as its paraxial imaging theory and practical design methods like multi-parametric optimization techniques. Although these imaging optical design methods can provide elegant solutions to many traditional optical problems, there are more and more new design problems, like solar concentrator, illumination system, ultra-compact camera, etc., that require maximum energy transfer efficiency, or ultra-compact optical structure. These problems do not have simple solutions from classical imaging design methods, because not only paraxial rays, but also non-paraxial rays should be well considered in the design process. Non-imaging optics is a newly developed optical discipline, which does not aim to form images, but to maximize energy transfer efficiency. One important concept developed from non-imaging optics is the “edge-ray principle”, which states that the energy flow contained in a bundle of rays will be transferred to the target, if all its edge rays are transferred to the target. Based on that concept, many CPC solar concentrators have been developed with efficiency close to the thermodynamic limit. When more than one bundle of edge-rays needs to be considered in the design, one way to obtain solutions is to use SMS method. SMS stands for Simultaneous Multiple Surface, which means several optical surfaces are constructed simultaneously. The SMS method was developed as a design method in Non-imaging optics during the 90s. The method can be considered as an extension to the Cartesian Oval calculation. In the traditional Cartesian Oval calculation, one optical surface is built to transform an input wave-front to an out-put wave-front. The SMS method however, is dedicated to solve more than 1 wave-fronts transformation problem. In the beginning, only 2 input wave-fronts and 2 output wave-fronts transformation problem was considered in the SMS design process for rotational optical systems or free-form optical systems. Usually “SMS 2D” method stands for the SMS procedure developed for rotational optical system, and “SMS 3D” method for the procedure for free-form optical system. Although the SMS method was originally employed in non-imaging optical system designs, it has been found during this thesis that with the improved capability to design more surfaces and control more input and output wave-fronts, the SMS method can also be applied to imaging system designs and possesses great advantage over traditional design methods. In this thesis, one of the main goals to achieve is to further develop the existing SMS-2D method to design with more surfaces and improve the stability of the SMS-2D and SMS-3D algorithms, so that further optimization process can be combined with SMS algorithms. The benefits of SMS plus optimization strategy over traditional optimization strategy will be explained in details for both rotational and free-form imaging optical system designs. Another main goal is to develop novel design concepts and methods suitable for challenging non-imaging applications, e.g. solar concentrator and solar tracker. This thesis comprises 9 chapters and can be grouped into two parts: the first part (chapter 2-5) contains research works in the imaging field, and the second part (chapter 6-8) contains works in the non-imaging field. In the first chapter, an introduction to basic imaging and non-imaging design concepts and theories is given. Chapter 2 presents a basic SMS-2D imaging design procedure using meridian rays. In this chapter, we will set the imaging design problem from the SMS point of view, and try to solve the problem numerically. The stability of this SMS-2D design procedure will also be discussed. The design concepts and procedures developed in this chapter lay the path for further improvement. Chapter 3 presents two improved SMS 3 surfaces’ design procedures using meridian rays (SMS-3M) and skew rays (SMS-1M2S) respectively. The major improvement has been made to the central segments selections, so that the whole SMS procedures become more stable compared to procedures described in Chapter 2. Since these two algorithms represent two types of phase space sampling, their image forming capabilities are compared in a simple objective design. Chapter 4 deals with an ultra-compact SWIR camera design with the SMS-3M method. The difficulties in this wide band camera design is how to maintain high image quality meanwhile reduce the overall system length. This interesting camera design provides a playground for the classical design method and SMS design methods. We will show designs and optical performance from both classical design method and the SMS design method. Tolerance study is also given as the end of the chapter. Chapter 5 develops a two-stage SMS-3D based optimization strategy for a 2 freeform mirrors imaging system. In the first optimization phase, the SMS-3D method is integrated into the optimization process to construct the two mirrors in an accurate way, drastically reducing the unknown parameters to only few system configuration parameters. In the second optimization phase, previous optimized mirrors are parameterized into Qbfs type polynomials and set up in code V. Code V optimization results demonstrates the effectiveness of this design strategy in this 2-mirror system design. Chapter 6 shows an etendue-squeezing condenser optics, which were prepared for the 2010 IODC illumination contest. This interesting design employs many non-imaging techniques such as the SMS method, etendue-squeezing tessellation, and groove surface design. This device has theoretical efficiency limit as high as 91.9%. Chapter 7 presents a freeform mirror-type solar concentrator with uniform irradiance on the solar cell. Traditional parabolic mirror concentrator has many drawbacks like hot-pot irradiance on the center of the cell, insufficient use of active cell area due to its rotational irradiance pattern and small acceptance angle. In order to conquer these limitations, a novel irradiance homogenization concept is developed, which lead to a free-form mirror design. Simulation results show that the free-form mirror reflector has rectangular irradiance pattern, uniform irradiance distribution and large acceptance angle, which confirm the viability of the design concept. Chapter 8 presents a novel beam-steering array optics design strategy. The goal of the design is to track large angle parallel rays by only moving optical arrays laterally, and convert it to small angle parallel output rays. The design concept is developed as an extended SMS method. Potential applications of this beam-steering device are: skylights to provide steerable natural illumination, building integrated CPV systems, and steerable LED illumination. Conclusion and future lines of work are given in Chapter 9. Resumen La óptica de formación de imagen clásica se ha ido desarrollando durante siglos, dando lugar tanto a la teoría de óptica paraxial y los métodos de diseño prácticos como a técnicas de optimización multiparamétricas. Aunque estos métodos de diseño óptico para formación de imagen puede aportar soluciones elegantes a muchos problemas convencionales, siguen apareciendo nuevos problemas de diseño óptico, concentradores solares, sistemas de iluminación, cámaras ultracompactas, etc. que requieren máxima transferencia de energía o dimensiones ultracompactas. Este tipo de problemas no se pueden resolver fácilmente con métodos clásicos de diseño porque durante el proceso de diseño no solamente se deben considerar los rayos paraxiales sino también los rayos no paraxiales. La óptica anidólica o no formadora de imagen es una disciplina que ha evolucionado en gran medida recientemente. Su objetivo no es formar imagen, es maximazar la eficiencia de transferencia de energía. Un concepto importante de la óptica anidólica son los “rayos marginales”, que se pueden utilizar para el diseño de sistemas ya que si todos los rayos marginales llegan a nuestra área del receptor, todos los rayos interiores también llegarán al receptor. Haciendo uso de este principio, se han diseñado muchos concentradores solares que funcionan cerca del límite teórico que marca la termodinámica. Cuando consideramos más de un haz de rayos marginales en nuestro diseño, una posible solución es usar el método SMS (Simultaneous Multiple Surface), el cuál diseña simultáneamente varias superficies ópticas. El SMS nació como un método de diseño para óptica anidólica durante los años 90. El método puede ser considerado como una extensión del cálculo del óvalo cartesiano. En el método del óvalo cartesiano convencional, se calcula una superficie para transformar un frente de onda entrante a otro frente de onda saliente. El método SMS permite transformar varios frentes de onda de entrada en frentes de onda de salida. Inicialmente, sólo era posible transformar dos frentes de onda con dos superficies con simetría de rotación y sin simetría de rotación, pero esta limitación ha sido superada recientemente. Nos referimos a “SMS 2D” como el método orientado a construir superficies con simetría de rotación y llamamos “SMS 3D” al método para construir superficies sin simetría de rotación o free-form. Aunque el método originalmente fue aplicado en el diseño de sistemas anidólicos, se ha observado que gracias a su capacidad para diseñar más superficies y controlar más frentes de onda de entrada y de salida, el SMS también es posible aplicarlo a sistemas de formación de imagen proporcionando una gran ventaja sobre los métodos de diseño tradicionales. Uno de los principales objetivos de la presente tesis es extender el método SMS-2D para permitir el diseño de sistemas con mayor número de superficies y mejorar la estabilidad de los algoritmos del SMS-2D y SMS-3D, haciendo posible combinar la optimización con los algoritmos. Los beneficios de combinar SMS y optimización comparado con el proceso de optimización tradicional se explican en detalle para sistemas con simetría de rotación y sin simetría de rotación. Otro objetivo importante de la tesis es el desarrollo de nuevos conceptos de diseño y nuevos métodos en el área de la concentración solar fotovoltaica. La tesis está estructurada en 9 capítulos que están agrupados en dos partes: la primera de ellas (capítulos 2-5) se centra en la óptica formadora de imagen mientras que en la segunda parte (capítulos 6-8) se presenta el trabajo del área de la óptica anidólica. El primer capítulo consta de una breve introducción de los conceptos básicos de la óptica anidólica y la óptica en formación de imagen. El capítulo 2 describe un proceso de diseño SMS-2D sencillo basado en los rayos meridianos. En este capítulo se presenta el problema de diseñar un sistema formador de imagen desde el punto de vista del SMS y se intenta obtener una solución de manera numérica. La estabilidad de este proceso se analiza con detalle. Los conceptos de diseño y los algoritmos desarrollados en este capítulo sientan la base sobre la cual se realizarán mejoras. El capítulo 3 presenta dos procedimientos para el diseño de un sistema con 3 superficies SMS, el primero basado en rayos meridianos (SMS-3M) y el segundo basado en rayos oblicuos (SMS-1M2S). La mejora más destacable recae en la selección de los segmentos centrales, que hacen más estable todo el proceso de diseño comparado con el presentado en el capítulo 2. Estos dos algoritmos representan dos tipos de muestreo del espacio de fases, su capacidad para formar imagen se compara diseñando un objetivo simple con cada uno de ellos. En el capítulo 4 se presenta un diseño ultra-compacto de una cámara SWIR diseñada usando el método SMS-3M. La dificultad del diseño de esta cámara de espectro ancho radica en mantener una alta calidad de imagen y al mismo tiempo reducir drásticamente sus dimensiones. Esta cámara es muy interesante para comparar el método de diseño clásico y el método de SMS. En este capítulo se presentan ambos diseños y se analizan sus características ópticas. En el capítulo 5 se describe la estrategia de optimización basada en el método SMS-3D. El método SMS-3D calcula las superficies ópticas de manera precisa, dejando sólo unos pocos parámetros libres para decidir la configuración del sistema. Modificando el valor de estos parámetros se genera cada vez mediante SMS-3D un sistema completo diferente. La optimización se lleva a cabo variando los mencionados parámetros y analizando el sistema generado. Los resultados muestran que esta estrategia de diseño es muy eficaz y eficiente para un sistema formado por dos espejos. En el capítulo 6 se describe un sistema de compresión de la Etendue, que fue presentado en el concurso de iluminación del IODC en 2010. Este interesante diseño hace uso de técnicas propias de la óptica anidólica, como el método SMS, el teselado de las lentes y el diseño mediante grooves. Este dispositivo tiene un límite teórica en la eficiencia del 91.9%. El capítulo 7 presenta un concentrador solar basado en un espejo free-form con irradiancia uniforme sobre la célula. Los concentradores parabólicos tienen numerosas desventajas como los puntos calientes en la zona central de la célula, uso no eficiente del área de la célula al ser ésta cuadrada y además tienen ángulos de aceptancia de reducido. Para poder superar estas limitaciones se propone un novedoso concepto de homogeneización de la irrandancia que se materializa en un diseño con espejo free-form. El análisis mediante simulación demuestra que la irradiancia es homogénea en una región rectangular y con mayor ángulo de aceptancia, lo que confirma la viabilidad del concepto de diseño. En el capítulo 8 se presenta un novedoso concepto para el diseño de sistemas afocales dinámicos. El objetivo del diseño es realizar un sistema cuyo haz de rayos de entrada pueda llegar con ángulos entre ±45º mientras que el haz de rayos a la salida sea siempre perpendicular al sistema, variando únicamente la posición de los elementos ópticos lateralmente. Las aplicaciones potenciales de este dispositivo son varias: tragaluces que proporcionan iluminación natural, sistemas de concentración fotovoltaica integrados en los edificios o iluminación direccionable con LEDs. Finalmente, el último capítulo contiene las conclusiones y las líneas de investigación futura.

Free-form optical systems for nonimaging applications : Sistemas ópticos anamórficos para aplicaciones anidólicas

La óptica anidólica es una rama de la óptica cuyo desarrollo comenzó a mediados de la década de 1960. Este relativamente nuevo campo de la óptica se centra en la transferencia eficiente de la luz, algo necesario en muchas aplicaciones, entre las que destacamos los concentradores solares y los sistemas de iluminación. Las soluciones de la óptica clásica a los problemas de la transferencia de energía de la luz sólo son adecuadas cuando los rayos de luz son paraxiales. La condición paraxial no se cumple en la mayoría de las aplicaciones para concentración e iluminación. Esta tesis contiene varios diseños free-form (aquellos que no presentan ninguna simetría, ni de rotación ni lineal) cuyas aplicaciones van destinadas a estos dos campos. El término nonimaging viene del hecho de que estos sistemas ópticos no necesitan formar una imagen del objeto, aunque no formar la imagen no es una condición necesaria. Otra palabra que se utiliza a veces en lugar de nonimaging es la palabra anidólico, viene del griego "an+eidolon" y tiene el mismo significado. La mayoría de los sistemas ópticos diseñados para aplicaciones anidólicas no presentan ninguna simetría, es decir, son free-form (anamórficos). Los sistemas ópticos free-form están siendo especialmente relevantes durante los últimos años gracias al desarrollo de las herramientas para su fabricación como máquinas de moldeo por inyección y el mecanizado multieje. Sin embargo, solo recientemente se han desarrollado técnicas de diseño anidólicas capaces de cumplir con estos grados de libertad. En aplicaciones de iluminación el método SMS3D permite diseñar dos superficies free-form para controlar las fuentes de luz extensas. En los casos en que se requiere una elevada asimetría de la fuente, el objeto o las restricciones volumétricos, las superficies free-form permiten obtener soluciones de mayor eficiencia, o disponer de menos elementos en comparación con las soluciones de simetría de rotación, dado que las superficies free-form tienen más grados de libertad y pueden realizar múltiples funciones debido a su naturaleza anamórfica. Los concentradores anidólicos son muy adecuados para la captación de energía solar, ya que el objetivo no es la reproducción de una imagen exacta del sol, sino sencillamente la captura de su energía. En este momento, el campo de la concentración fotovoltaica (CPV) tiende hacia sistemas de alta concentración con el fin de compensar el gasto de las células solares multi-unión (MJ) utilizadas como receptores, reduciendo su área. El interés en el uso de células MJ radica en su alta eficiencia de conversión. Para obtener sistemas competitivos en aplicaciones terrestres se recurre a sistemas fotovoltaicos de alta concentración (HCPV), con factores de concentración geométrica por encima de 500x. Estos sistemas se componen de dos (o más) elementos ópticos (espejos y/o lentes). En los sistemas presentados a lo largo de este trabajo se presentan ejemplos de concentradores HCPV con elementos reflexivos como etapa primaria, así como concentradores con elementos refractivos (lente de Fresnel). Con la necesidad de aumentar la eficiencia de los sistemas HCPV reales y con el fin de proporcionar la división más eficiente del espectro solar, células conteniendo cuatro o más uniones (con un potencial de alcanzar eficiencias de más del 45% a una concentración de cientos de soles) se exploran hoy en día. En esta tesis se presenta una de las posibles arquitecturas de división del espectro (spectrum-splitting en la literatura anglosajona) que utilizan células de concentración comercial. Otro campo de aplicación de la óptica nonimaging es la iluminación, donde es necesario proporcionar un patrón de distribución de la iluminación específico. La iluminación de estado sólido (SSL), basada en la electroluminiscencia de materiales semiconductores, está proporcionando fuentes de luz para aplicaciones de iluminación general. En la última década, los diodos emisores de luz (LED) de alto brillo han comenzado a reemplazar a las fuentes de luz convencionales debido a la superioridad en la calidad de la luz emitida, elevado tiempo de vida, compacidad y ahorro de energía. Los colimadores utilizados con LEDs deben cumplir con requisitos tales como tener una alta eficiencia, un alto control del haz de luz, una mezcla de color espacial y una gran compacidad. Presentamos un colimador de luz free-form con microestructuras capaz de conseguir buena colimación y buena mezcla de colores con una fuente de LED RGGB. Una buena mezcla de luz es importante no sólo para simplificar el diseño óptico de la luminaria sino también para evitar hacer binning de los chips. La mezcla de luz óptica puede reducir los costes al evitar la modulación por ancho de pulso y otras soluciones electrónicas patentadas para regulación y ajuste de color. Esta tesis consta de cuatro capítulos. Los capítulos que contienen la obra original de esta tesis son precedidos por un capítulo introductorio donde se presentan los conceptos y definiciones básicas de la óptica geométrica y en el cual se engloba la óptica nonimaging. Contiene principios de la óptica no formadora de imagen junto con la descripción de sus problemas y métodos de diseño. Asimismo se describe el método de Superficies Múltiples Simultáneas (SMS), que destaca por su versatilidad y capacidad de controlar varios haces de rayos. Adicionalmente también se describe la integración Köhler y sus aplicaciones en el campo de la energía fotovoltaica. La concentración fotovoltaica y la iluminación de estado sólido son introducidas junto con la revisión de su estado actual. El Segundo y Tercer Capítulo contienen diseños ópticos avanzados con aplicación en la concentración solar principalmente, mientras que el Cuarto Capítulo describe el colimador free-form con surcos que presenta buena mezcla de colores para aplicaciones de iluminación. El Segundo Capítulo describe dos concentradores ópticos HCPV diseñados con el método SMS en tres dimensiones (SMS3D) que llevan a cabo integración Köhler en dos direcciones con el fin de proporcionar una distribución de irradiancia uniforme libre de aberraciones cromáticas sobre la célula solar. Uno de los diseños es el concentrador XXR free-form diseñado con el método SMS3D, donde el espejo primario (X) y la lente secundaria (R) se dividen en cuatro sectores simétricos y llevan a cabo la integración Köhler (proporcionando cuatro unidades del array Köhler), mientras que el espejo intermedio (X) presenta simetría rotacional. Otro concentrador HCPV presentado es el Fresnel-RXI (FRXI) con una lente de Fresnel funcionando como elemento primario (POE) y una lente RXI como elemento óptico secundario (SOE), que presenta configuración 4-fold con el fin de realizar la integración Köhler. Las lentes RXI son dispositivos nonimaging conocidos, pero su aplicación como elemento secundario es novedosa. Los concentradores XXR y FRXI Köhler son ejemplos académicos de muy alta concentración (más de 2,000x, mientras que los sistemas convencionales hoy en día no suelen llegar a 1,000x) preparados para las células solares N-unión (con N>3), que probablemente requerirán una mayor concentración y alta uniformidad espectral de irradiancia con el fin de obtener sistemas CPV terrestres eficientes y rentables. Ambos concentradores están diseñados maximizando funciones de mérito como la eficiencia óptica, el producto concentración-aceptancia (CAP) y la uniformidad de irradiancia sobre la célula libre de la aberración cromática (integración Köhler). El Tercer Capítulo presenta una arquitectura para la división del espectro solar basada en un módulo HCPV con alta concentración (500x) y ángulo de aceptancia alto (>1º) que tiene por objeto reducir ambas fuentes de pérdidas de las células triple unión (3J) comerciales: el uso eficiente del espectro solar y la luz reflejada de los contactos metálicos y de la superficie de semiconductor. El módulo para la división del espectro utiliza el espectro solar más eficiente debido a la combinación de una alta eficiencia de una célula de concentración 3J (GaInP/GaInAs/Ge) y una de contacto posterior (BPC) de concentración de silicio (Si), así como la técnica de confinamiento externo para la recuperación de la luz reflejada por la célula 3J con el fin de ser reabsorbida por la célula. En la arquitectura propuesta, la célula 3J opera con su ganancia de corriente optimizada (concentración geométrica de 500x), mientras que la célula de silicio trabaja cerca de su óptimo también (135x). El módulo de spectrum-splitting consta de una lente de Fresnel plana como POE y un concentrador RXI free-form como SOE con un filtro paso-banda integrado en él. Tanto POE como SOE realizan la integración Köhler para producir homogeneización de luz sobre la célula. El filtro paso banda envía los fotones IR en la banda 900-1,150nm a la célula de silicio. Hay varios aspectos prácticos de la arquitectura del módulo presentado que ayudan a reducir la complejidad de los sistemas spectrum-splitting (el filtro y el secundario forman una sola pieza sólida, ambas células son coplanarias simplificándose el cableado y la disipación de calor, etc.). Prototipos prueba-de-concepto han sido ensamblados y probados a fin de demostrar la fabricabilidad del filtro y su rendimiento cuando se combina con la técnica de reciclaje de luz externa. Los resultados obtenidos se ajustan bastante bien a los modelos y a las simulaciones e invitan al desarrollo de una versión más compleja de este prototipo en el futuro. Dos colimadores sólidos con surcos free-form se presentan en el Cuarto Capítulo. Ambos diseños ópticos están diseñados originalmente usando el método SMS3D. La segunda superficie ópticamente activa está diseñada a posteriori como una superficie con surcos. El diseño inicial de dos espejos (XX) está diseñado como prueba de concepto. En segundo lugar, el diseño RXI free-form es comparable con los colimadores RXI existentes. Se trata de un diseño muy compacto y eficiente que proporciona una muy buena mezcla de colores cuando funciona con LEDs RGB fuera del eje óptico como en los RGB LEDs convencionales. Estos dos diseños son dispositivos free-form diseñados con la intención de mejorar las propiedades de mezcla de colores de los dispositivos no aplanáticos RXI con simetría de revolución y la eficiencia de los aplanáticos, logrando una buena colimación y una buena mezcla de colores. La capacidad de mezcla de colores del dispositivo no-aplanático mejora añadiendo características de un aplanático a su homólogo simétrico sin pérdida de eficiencia. En el caso del diseño basado en RXI, su gran ventaja consiste en su menor coste de fabricación ya que el proceso de metalización puede evitarse. Aunque algunos de los componentes presentan formas muy complejas, los costes de fabricación son relativamente insensibles a la complejidad del molde, especialmente en el caso de la producción en masa (tales como inyección de plástico), ya que el coste del molde se reparte entre todas las piezas fabricadas. Por último, las últimas dos secciones son las conclusiones y futuras líneas de investigación. ABSTRACT Nonimaging optics is a branch of optics whose development began in the mid-1960s. This rather new field of optics focuses on the efficient light transfer necessary in many applications, among which we highlight solar concentrators and illumination systems. The classical optics solutions to the problems of light energy transfer are only appropriate when the light rays are paraxial. The paraxial condition is not met in most applications for the concentration and illumination. This thesis explores several free-form designs (with neither rotational nor linear symmetry) whose applications are intended to cover the above mentioned areas and more. The term nonimaging comes from the fact that these optical systems do not need to form an image of the object, although it is not a necessary condition not to form an image. Another word sometimes used instead of nonimaging is anidolic, and it comes from the Greek “an+eidolon” and has the same meaning. Most of the optical systems designed for nonimaging applications are without any symmetry, i.e. free-form. Free-form optical systems become especially relevant lately with the evolution of free-form tooling (injection molding machines, multi-axis machining techniques, etc.). Nevertheless, only recently there are nonimaging design techniques that are able to meet these degrees of freedom. In illumination applications, the SMS3D method allows designing two free-form surfaces to control very well extended sources. In cases when source, target or volumetric constrains have very asymmetric requirements free-form surfaces are offering solutions with higher efficiency or with fewer elements in comparison with rotationally symmetric solutions, as free-forms have more degrees of freedom and they can perform multiple functions due to their free-form nature. Anidolic concentrators are well suited for the collection of solar energy, because the goal is not the reproduction of an exact image of the sun, but instead the collection of its energy. At this time, Concentration Photovoltaics (CPV) field is turning to high concentration systems in order to compensate the expense of multi-junction (MJ) solar cells used as receivers by reducing its area. Interest in the use of MJ cells lies in their very high conversion efficiency. High Concentration Photovoltaic systems (HCPV) with geometric concentration of more than 500x are required in order to have competitive systems in terrestrial applications. These systems comprise two (or more) optical elements, mirrors and/or lenses. Systems presented in this thesis encompass both main types of HCPV architectures: concentrators with primary reflective element and concentrators with primary refractive element (Fresnel lens). Demand for the efficiency increase of the actual HCPV systems as well as feasible more efficient partitioning of the solar spectrum, leads to exploration of four or more junction solar cells or submodules. They have a potential of reaching over 45% efficiency at concentration of hundreds of suns. One possible architectures of spectrum splitting module using commercial concentration cells is presented in this thesis. Another field of application of nonimaging optics is illumination, where a specific illuminance distribution pattern is required. The Solid State Lighting (SSL) based on semiconductor electroluminescence provides light sources for general illumination applications. In the last decade high-brightness Light Emitting Diodes (LEDs) started replacing conventional light sources due to their superior output light quality, unsurpassed lifetime, compactness and energy savings. Collimators used with LEDs have to meet requirements like high efficiency, high beam control, color and position mixing, as well as a high compactness. We present a free-form collimator with microstructures that performs good collimation and good color mixing with RGGB LED source. Good light mixing is important not only for simplifying luminaire optical design but also for avoiding die binning. Optical light mixing may reduce costs by avoiding pulse-width modulation and other patented electronic solutions for dimming and color tuning. This thesis comprises four chapters. Chapters containing the original work of this thesis are preceded by the introductory chapter that addresses basic concepts and definitions of geometrical optics on which nonimaging is developed. It contains fundamentals of nonimaging optics together with the description of its design problems, principles and methods, and with the Simultaneous Multiple Surface (SMS) method standing out for its versatility and ability to control several bundles of rays. Köhler integration and its applications in the field of photovoltaics are described as well. CPV and SSL fields are introduced together with the review on their background and their current status. Chapter 2 and Chapter 3 contain advanced optical designs with primarily application in solar concentration; meanwhile Chapter 4 portrays the free-form V-groove collimator with good color mixing property for illumination application. Chapter 2 describes two HCPV optical concentrators designed with the SMS method in three dimensions (SMS3D). Both concentrators represent Köhler integrator arrays that provide uniform irradiance distribution free from chromatic aberrations on the solar cell. One of the systems is the XXR free-form concentrator designed with the SMS3D method. The primary mirror (X) of this concentrator and secondary lens (R) are divided in four symmetric sectors (folds) that perform Köhler integration; meanwhile the intermediate mirror (X) is rotationally symmetric. Second HCPV concentrator is the Fresnel-RXI (FRXI) with flat Fresnel lens as the Primary Optical Element (POE) and an RXI lens as the Secondary Optical Element (SOE). This architecture manifests 4-fold configuration for performing Köhler integration (4 array units), as well. The RXI lenses are well-known nonimaging devices, but their application as SOE is novel. Both XXR and FRXI Köhler HCPV concentrators are academic examples of very high concentration (more than 2,000x meanwhile conventional systems nowadays have up to 1,000x) prepared for the near future N-junction (N>3) solar cells. In order to have efficient and cost-effective terrestrial CPV systems, those cells will probably require higher concentrations and high spectral irradiance uniformity. Both concentrators are designed by maximizing merit functions: the optical efficiency, concentration-acceptance angle (CAP) and cell-irradiance uniformity free from chromatic aberrations (Köhler integration). Chapter 3 presents the spectrum splitting architecture based on a HCPV module with high concentration (500x) and high acceptance angle (>1º). This module aims to reduce both sources of losses of the actual commercial triple-junction (3J) solar cells with more efficient use of the solar spectrum and with recovering the light reflected from the 3J cells’ grid lines and semiconductor surface. The solar spectrum is used more efficiently due to the combination of a high efficiency 3J concentration cell (GaInP/GaInAs/Ge) and external Back-Point-Contact (BPC) concentration silicon (Si) cell. By employing external confinement techniques, the 3J cell’s reflections are recovered in order to be re-absorbed by the cell. In the proposed concentrator architecture, the 3J cell operates at its optimized current gain (at geometrical concentration of 500x), while the Si cell works near its optimum, as well (135x). The spectrum splitting module consists of a flat Fresnel lens (as the POE), and a free-form RXI-type concentrator with a band-pass filter embedded in it (as the SOE), both POE and SOE performing Köhler integration to produce light homogenization. The band-pass filter sends the IR photons in the 900-1,150nm band to the Si cell. There are several practical aspects of presented module architecture that help reducing the added complexity of the beam splitting systems: the filter and secondary are forming a single solid piece, both cells are coplanar so the heat management and wiring is simplified, etc. Two proof-of-concept prototypes are assembled and tested in order to prove filter manufacturability and performance, as well as the potential of external light recycling technique. Obtained measurement results agree quite well with models and simulations, and show an opened path to manufacturing of the Fresnel RXI-type secondary concentrator with spectrum splitting strategy. Two free-form solid V-groove collimators are presented in Chapter 4. Both free-form collimators are originally designed with the SMS3D method. The second mirrored optically active surface is converted in a grooved surface a posteriori. Initial two mirror (XX) design is presented as a proof-of-concept. Second, RXI free-form design is comparable with existing RXI collimators as it is a highly compact and a highly efficient design. It performs very good color mixing of the RGGB LED sources placed off-axis like in conventional RGB LEDs. Collimators described here improve color mixing property of the prior art rotationally symmetric no-aplanatic RXI devices, and the efficiency of the aplanatic ones, accomplishing both good collimation and good color mixing. Free-form V-groove collimators enhance the no-aplanatic device's blending capabilities by adding aplanatic features to its symmetric counterpart with no loss in efficiency. Big advantage of the RXI design is its potentially lower manufacturing cost, since the process of metallization may be avoided. Although some components are very complicated for shaping, the manufacturing costs are relatively insensitive to the complexity of the mold especially in the case of mass production (such as plastic injection), as the cost of the mold is spread in many parts. Finally, last two sections are conclusions and future lines of investigation.