Fluorinated compounds are environmentally persistent and have been demonstrated to bioaccumulate and contribute to climate change. The focus of this work was to better understand the atmospheric chemistry of poly- and per-fluorinated compounds in order to appreciate their impacts on the environment. Several fluorinated compounds exist for which data on climate impacts do not exist. Radiative efficiencies (REs) and atmospheric lifetimes of two new long-lived greenhouse gases (LLGHGs) were determined using smog chamber techniques: perfluoropolyethers and perfluoroalkyl amines. Through this, it was observed that RE was not directly related to the number of carbon-fluorine bonds. A structure-activity relationship was created to allow the determination of RE solely from the chemical structure of the compound. Also, a novel method was developed to detect polyfluorinated LLGHGs in the atmosphere. Using carbotrap, thermal desorption and cryogenic extraction coupled to GC-MS, atmospheric measurements can be made for a number of previously undetected compounds. A perfluoroalkyl amine was detected in the atmosphere using this technique, which is the compound with the highest RE ever detected in the atmosphere. Perfluorocarboxylic acids (PFCAs) are water soluble and non-volatile, suggesting they are not susceptible to long-range transport. A hypothesis was derived to explain the ubiquitous distribution of these compounds involving atmospheric formation of PFCAs from volatile precursors. Using smog chamber techniques with offline analysis, perfluorobutenes and fluorotelomer iodides were shown to yield PFCAs from atmospheric oxidation. Dehydrofluorination of perfluorinated alcohols (PFOHs) is poorly understood in the mechanism of PFCA atmospheric formation. Using density functional techniques, overtone-induced photolysis was shown to lead to dehydrofluorination of PFOHs. In the presence of water, this mechanism could be a sink of PFOHs in the atmosphere. Confirmation of the importance of volatile precursors was derived from examination of snow from High Arctic ice caps. This provided the first empirical evidence of atmospheric deposition. Through the analytes observed, fluxes and temporal trends, it was concluded that atmospheric oxidation of volatile precursors is an important source of PFCAs to the Arctic.

Fluorinated compounds are environmentally persistent and have been demonstrated to bioaccumulate and contribute to climate change. The focus of this work was to better understand the atmospheric chemistry of poly- and per-fluorinated compounds in order to appreciate their impacts on the environment. Several fluorinated compounds exist for which data on climate impacts do not exist. Radiative efficiencies (REs) and atmospheric lifetimes of two new long-lived greenhouse gases (LLGHGs) were determined using smog chamber techniques: perfluoropolyethers and perfluoroalkyl amines. Through this, it was observed that RE was not directly related to the number of carbon-fluorine bonds. A structure-activity relationship was created to allow the determination of RE solely from the chemical structure of the compound. Also, a novel method was developed to detect polyfluorinated LLGHGs in the atmosphere. Using carbotrap, thermal desorption and cryogenic extraction coupled to GC-MS, atmospheric measurements can be made for a number of previously undetected compounds. A perfluoroalkyl amine was detected in the atmosphere using this technique, which is the compound with the highest RE ever detected in the atmosphere. Perfluorocarboxylic acids (PFCAs) are water soluble and non-volatile, suggesting they are not susceptible to long-range transport. A hypothesis was derived to explain the ubiquitous distribution of these compounds involving atmospheric formation of PFCAs from volatile precursors. Using smog chamber techniques with offline analysis, perfluorobutenes and fluorotelomer iodides were shown to yield PFCAs from atmospheric oxidation. Dehydrofluorination of perfluorinated alcohols (PFOHs) is poorly understood in the mechanism of PFCA atmospheric formation. Using density functional techniques, overtone-induced photolysis was shown to lead to dehydrofluorination of PFOHs. In the presence of water, this mechanism could be a sink of PFOHs in the atmosphere. Confirmation of the importance of volatile precursors was derived from examination of snow from High Arctic ice caps. This provided the first empirical evidence of atmospheric deposition. Through the analytes observed, fluxes and temporal trends, it was concluded that atmospheric oxidation of volatile precursors is an important source of PFCAs to the Arctic.

Dans cette thèse, nous analysons les principales caractéristiques des aérosols atmosphériques sur un site urbain en Afrique de l’Ouest : la ville de Ouagadougou. Cette analyse est suivie de l’évaluation du forçage radiatif produit par cette population d’aérosols au sommet de l’atmosphère, dans la couche atmosphérique ainsi qu’à la surface terrestre. Une étude climatologique des propriétés optiques (épaisseurs optiques, exposant d’Angström, albédo de simple diffusion, facteur d’asymétrie) et microphysiques (distribution granulométrique, indice complexe de réfraction) a été effectuée sur la base des données de mesures et d’inversions photométriques du réseau AERONET. L’analyse de ces données a permis de définir à diverses échelles de temps les différentes variabilités des propriétés étudiées. Ces propriétés ont mis en exergue les effets combinés de l’activité anthropique, du cycle de production des poussières minérales d’origine saharienne, de la succession saisonnière et la dynamique du climat spécifiques à cette région de la terre. La composition du panache d’aérosols a également été déduite de l’analyse des données optiques, et les conclusions tirées se sont avérées être en bon accord avec des mesures chimiques effectuées au LSCE sur des échantillons obtenus par prélèvement manuel sur filtres. Le bilan radiatif a été évalué en utilisant le modèle GAME. Cette simulation a montré une forte corrélation du forçage avec la succession des saisons sèche et humide, avec des valeurs extrêmes au mois d’Août (humide) et de Mars (sec avec poussières maximales). Les résultats traduisent un refroidissement en surface pouvant atteindre -41 W/m 2 en Mars, un réchauffement de la couche atmosphérique qui va de 15 à 35 W/m 2 environ et un refroidissement au sommet de l’atmosphère compris entre -2 et -6 W/m 2 . La représentation du forçage calculé en fonction de l’albédo de simple diffusion a montré une tendance linéaire avec un coefficient de corrélation traduisant une fiabilité de nos résultats de l’ordre de 88%. La cohérence des valeurs simulées a été aussi montrée par une comparaison avec des résultats obtenus dans la région Ouest Africaine par d’autres chercheurs utilisant des techniques différentes. De même, la représentation de l’efficacité radiative simulée en fonction de celle inversée par AERONET a montré un très bon accord. / In this thesis, we analyze the main characteristics of atmospheric aerosols on an urban site in West Africa: Ouagadougou. This analysis is followed by an assessment of the radiative forcing produced by this population of aerosols at the top of the atmosphere, in the atmospheric layer and at the Earth's surface. A climatological study of the optical properties (optical thickness, Angstrom exponent, single scattering albedo, asymmetry factor) and microphysical properties (particle size distribution, complex refractive index) was performed on basis of data obtained from photometric measurement and inversions of AERONET network. The analysis of these data allowed us to define the different variabilities of the properties studied at various time scales. These properties have highlighted the combined effects of human activity, the cycle production of mineral dust from the Sahara region, the seasonal succession and the climate dynamics known in this region of the earth. The composition of the aerosol plume was also deduced from the analysis of optical data, and the conclusions were found to be in good agreement with chemical analysis carried out at LSCE on samples obtained by sampling on filters at Ouagadougou. The radiation balance was assessed using the GAME model. This simulation showed a strong relationship of the radiative forcing with the succesion of wet and dry seasons, with extreme values in August (wet) and Mars (dry with maximum dust emissions). The results showed a cooling at the surface that can reach -41 W / m 2 in March, a warming of the atmosphere, ranging from 15 to 35 W / m 2 about and a cooling at the top of the atmosphere between -2 and -6 W / m 2 . The representation of the radiative forcing calculated as a function of the single scattering albedo showed a linear trend with a correlation coefficient reflecting relatively good reliability of our results (about 88%). The consistency of simulated values was also shown by a comparison with the results obtained in the West African region by other researchers using different techniques. Similarly, the representation of the radiative efficiency simulated as a function of the inverted AERONET one showed a very good agreement.

Recombination mechanisms in gallium arsenide have been studied using temperature-dependent time-resolved photoluminescence-decay. New analytical methods are presented to improve the accuracy in bulk lifetime measurement, and these have been used to resolve the temperature-dependent lifetime. Fits to temperature-dependent lifetime yield measurement of the radiative-efficiency, revealing that samples grown by the Czochralski and molecular-beam-epitaxy methods are limited by radiative-recombination at 77K, with defect-mediated nonradiative-recombination becoming competitive at 300K and above. In samples grown with both doping types using molecular-beam-epitaxy, a common exponential increase in capture cross-section characterized by a high value of E_infinity=(258 +/- 1)meV was observed from the high-level injection lifetime over a wide temperature range (300-700K). This common signature was also observed from 500-600K in the hole-lifetime observed in n-type Czochralski GaAs where E_infinity=(261 +/- 7)meV was measured, which indicates that this signature parametrizes the exponential increase in hole-capture cross-section. The high E_infinity value rules out all candidate defects except for EL2, by comparison with hole-capture cross-section data previously measured by others using deep-level transient spectroscopy. / Thesis / Doctor of Philosophy (PhD)

La limite théorique de rendement des cellules photovoltaïques simple-jonction est de l’ordre de 33% d’après le modèle de Shockley-Queisser, ce qui reste éloigné de la limite de Carnot, prédisant une limite maximale de conversion énergie solaire → électricité de 93%. L’écart important entre ces deux limites découle des pertes intrinsèques, essentiellement liées à la conversion inefficace du spectre solaire et à la disparité entre les angles solides d’absorption et d’émission. Pour surmonter ces pertes et se rapprocher de la limite de Carnot, trois stratégies sont envisagées dans cette thèse : les cellules multi-jonction àconcentration, la combinaison de la concentration et de la restriction angulaire et les systèmes hybrides PV/CSP. Chacune de ces stratégies est limitée par des mécanismes qui dégradent leur performance.L’objectif de cette thèse est donc de comprendre dans quelle mesure les différents mécanismes limitants sont susceptibles d’affecter les performances des différentes stratégies étudiées, et d’optimiser l’architecture des cellules dans le but d’accroitre leur efficacité de conversion. Dans ce but, un modèle détaillé de cellule solaire tenant compte des principaux mécanismes limitant a été développé. Un outil d’optimisation par algorithme génétique a également été mis au point, afin d’explorer l’espace des différents paramètres étudiés pour identifier les conditions d’opération optimales. Nous démontrons l’importance majeure que revêt l’adaptation des propriétés optoélectroniques des matériaux utilisés aux conditions opératoires, que ce soit dans le cas des cellules solaires à concentration endurant des pertes résistives significatives, ou encore dans le cas de cellules solaires fonctionnant à des niveaux de températures très supérieurs à l’ambiante. Enfin, nous avons déterminé l’effet des principaux facteurs limitant que constituent les pertes résistives et les recombinaisons non-radiatives sur les cellules solairessimultanément soumises au flux solaire concentré et à la restriction angulaire du rayonnement émis. / The maximum efficiency limit attainable with a single-junction PV cell is ~ 33% according to the detailed balance formalism (also known as Shockley-Queisser model), which remains far from the Carnot limit, predicting a solar to electricity efficiency upper value of 93%. The large gap between both limits is due to intrinsic loss mechanisms, including the inefficient conversion of the solar spectrum and the large discrepancy between the solid angles of absorption and emission. To overcome these losses and get closer to the Carnot limit, three different strategies are considered in this thesis: concentrated multi-junction solarcells, the combination of solar concentration and angular confinement, and hybrid PV/CSP systems. Each strategy is inherently limited by several loss mechanisms that degrade their performances. The objective of this thesis is, hence, to better understand the extent to which these strategies are likely to be penalized by these losses, and to tailor the cell properties toward maximizing their efficiencies. To address these questions, a detailed-balance model of PV cell accounting for the main loss mechanisms was developed. A genetic-algorithm optimization tool was also implemented, aiming at exploring the parameter space and identifying the optimal operation conditions. We demonstrate the uttermost importance of tailoring the electronic properties of the materials used with both multi-junction solar cells undergoing significant series resistance losses, and PV cells operating at temperature levels exceeding ambient temperature. We also investigate the extent to which series resistances losses and non-radiative recombination are likely to affect the ability of PV cells simultaneously submitted to concentrated sunlight and angular restriction of the light emitted by band-to-band recombination.