This work concerns the microstructure of CSS-grown CdTe layers used for CdTe/CdS solar cells. Particular attention is given to how the development of microstructure on annealing with CdCl(_2) may correlate with increases in efficiency. By annealing pressed pellets of bulk CdTe powder, it is shown that microstructural change does occur on heating the material, enhanced by the inclusion of CdCl(_2) flux. However, the temperature required to cause significant effects is demonstrated to be higher than that at which heavy oxidation takes place. The dynamics of this oxidation are also examined. To investigate microstructural evolution in thin-films of CdTe, bi-layers of CdTe and CdS are examined by bevelling, thus revealing the microstructure to within ~1 µm of the interface. This allows optical microscopy and subsequent image analysis of grain structure. The work shows that the grain- size, which is well described by the Rayleigh distribution, varies linearly throughout the layer, but is invariant under CdCl(_2) treatment. Electrical measurements on these bi-layers, however, showed increased efficiency, as is widely reported. This demonstrates that the efficiency of these devices is not dictated by the bulk microstructure. Further, the region within 1 µm of the interface, of similar bi-layers to above, is examined by plan-view TEM. This reveals five-fold grain-growth on CdCl(_2) treatment. Moreover, these grains show a considerably smaller grain size than expected from extrapolating the linear trend in the bulk. These observations are explained in terms of the pinning of the CdTe grain size to the underlying CdS, and the small grain size this causes. A simple model was proposed for a link between the grain-growth to the efficiency improvement. The study also examines the behaviour of defects within grains upon CdCl(_2) treatment provided the first direct evidence of recovery on CdCl(_2) treatment in this system. Finally, a computer model is presented to describe the evolution of microstructure during growth. This is shown to be capable of reproducing the observed variation in grain size, but its strict physical accuracy is questioned.

This thesis contains primarily a study of CdTe/CdS heterojunction solar cells^ chiefly using photoluminescence spectroscopy. These solar cells show a good potential for commercial power generation in the near Aiture and are of interest to several major companies. A vital but little understood step in the manufacturing process is: annealing the cells in the presence of chlorine prior to back contact application. Studies are performed on a selection of thin film CdTe/CdS cells subjected to CdCl(_2) anneals of different duration. A chemical bevel etch was used to study the spectra at different depths into the sample and laser intensity arid sarhple temperature variations to identify the mechanisms behind the observed photoluminescence peaks. Evidence was found for the CdCl(_2) anneal promoting sulphur diffusion and subsequent grain boundary passivation in the CdTe, leading to increased minority carrier lifetimes and device efficiencies Attempts to obtain electroluminescence from the CdTe/CdS solar cells were madei By using current pulses electroluminescence was obtained in the 780-850nm range with discernible spectral features. Photoluminescence (PL) studies were also performed on a single crystal of CdTe grown to an unprecedented size of approx. 5 cm diameter at Durham university by a multi-tube seeded vapour method of crystal growth. Much higher resolution spectra were: obtained for this than for the solar cells. Several peaks were identified arid the mechanisms responsible were theorised. By taking slices of the crystal boule the PL spectra at different points-throughout the bulk of the crystal were determined. A series of high quality ion-implanted CdTe crystals were also studied! by intensity and temperature dependent PL in order to obtain a better understanding of the effects of known concentrations of known impurities on the PL spectra of CdTe. Specific PL features associated with certain dopants were observed.

Thesis (Ph. D. ) -- McMaster University, 1998. / Includes bibliographical references. Also available via World Wide Web.

Thesis (Ph.D.) -- University of Western Sydney, 2008. / A thesis submitted to the University of Western Sydney, College of Health and Science, Centre for Plant and Food Science, in fulfilment of the requirements for the degree of Doctor of Philosophy. Includes bibliographical references.

Thesis (Ph. D.)--University of Massachusetts Amherst, 2009. / Includes bibliographical references (p. 153-161). Print copy also available.

Malgré les avancées récentes, le cancer reste la première cause de mortalité en France avec ~ 150000 décès recensés par an (INCa 2012). Notamment, le cancer broncho-pulmonaire est l’un des plus agressifs, avec 29100 décès en 2011. La survie à cinq ans de seulement 10% des patients atteints des cancers du poumon non à petites cellules (NSCLC, 80% des cancers bronchiques), pose un problème d’ordre scientifique, médical et de santé publique. Il est communément admis qu’une sous-population de la tumeur acquiert en raison d’une instabilité génétique de nouvelles propriétés agressives nécessaires à sa dissémination, sa prolifération et une plus grande résistance aux chimiothérapies. Une meilleure compréhension de ces propriétés tumorales constitue un enjeu majeur pour prévenir à terme cette progression maligne. Nous avons axé notre recherche sur la macro-autophagie, un processus catabolique lysosomal essentiel à l’homéostasie cellulaire et sur un de ses substrats SQSTM1 (séquestosome ou p62). Au moment où j’ai initié ma thèse, une relation étroite entre l’autophagie, SQSTM1 et la progression tumorale venait d’être mise en lumière. Plusieurs membres de la machinerie autophagique sont fréquemment mutés/déletés dans les cancers. De façon paradoxale, l’autophagie peut également permettre la survie des cellules tumorales face à l’hypoxie, la carence nutritionnelle ou les chimiothérapies. / Despite recent advances, cancer remains the leading cause of death in France with~150,000 annual deaths (INCA, 2012). Notably, lung cancer is one of the most aggressive, with 29 100 deaths in 2011. The five-year survival is only 10 % of patients with lung cancer non-small cell (NSCLC, 80% of lung cancers), so it’s a medical/scientific challenge, and public health problem. Due to genetic instability, it’s commonly accepted that a subpopulation of tumor acquires new aggressive properties for its dissemination, its proliferation and greater resistance to chemotherapy. A better understanding of these tumor properties is a major issue to prevent this malignant progression. We focused our research on macro-autophagy, a lysosomal catabolic process essential for cellular homeostasis, and alos on one of its substrates SQSTM1 (Sequestosome or p62). When I started my PhD, a close relationship between autophagy, SQSTM1 and tumor progression had been highlighted. Several members of the autophagic machinery are frequently mutated/deleted in cancers. Paradoxically, autophagy can also allow the survival of tumor cells under hypoxia, nutritional deficiency or chemotherapy. How could we understand these conflicting functions, considering that the only autophagy substrates known are long half-lives proteins, damaged organelles and scaffold SQSTM1? Thus, SQSTM1 is essential for RasV12 driven oncogenesis (A Duran et al, Cancer Cell 2008).

Le cadmium (Cd) est un élément trace présent dans les sols agricoles qui contamine la chaîne alimentaire en étant prélevé par les plantes et accumulé dans les produits végétaux consommés. La biodisponibilité du Cd est un concept au cœur de l’évaluation des risques de transfert excessif du Cd du sol vers les plantes. Les plantes prélevant essentiellement l’ion Cd2+ dans la solution de sol, la biodisponibilité est fonction de deux principaux processus, la spéciation du Cd en solution (les différentes formes chimiques prises par le Cd en solution) et le partitionnement du Cd2+ entre la phase solide et la solution. L’objectif principal de ce travail a été d’élaborer des modèles simples à visée opérationnelle prédictifs de la concentration en Cd2+ dans la solution de sols agricoles, en modélisant soit la spéciation du Cd en solution de sol, soit le partitionnement phase solide-solution du Cd2+, celui-ci permettant de renseigner en outre la capacité de la phase à réapprovisionner la solution de sol lors de l’absorption racinaire. Nous avons également recherché des modèles pour la prédiction des teneurs en Cd2+ retrouvées dans les grains de blé dur. Nous avons développé deux approches de modélisation. La première, statistique, permet de produire des modèles simples à visée opérationnelle. La seconde, géochimique, permet de comprendre les mécanismes dominants et donc de juger de la cohérence de modèles statistiques simples pour représenter des processus physico-chimiques complexes. Ces deux approches ont montré de manière cohérente que pour les sols agricoles faiblement contaminés, le Cd qui s’échange entre la phase solide et la solution est vraisemblablement sorbé faiblement et peut-être estimé par le Cd extrait par NH4NO3 1 M minoré par une fraction fixée à des oxydes de manganèse. Les modélisations ont également montré l’importance du pH et de la teneur en Ca en solution comme variables contrôlant la solubilité de Cd2+, probablement en raison de leur rôle à régir la disponibilité des sites de sorption et de complexation vis-à-vis du Cd. Le modèle statistique le plus performant pour prédire la teneur en Cd dans le grain de blé dur reprend également ces variables, suggérant ainsi que les modèles statistiques simples de prédiction de la spéciation en solution et de partitionnement sol-solution du Cd sont des modèles pertinents pour estimer la biodisponibilité et qu’ils peuvent permettre de classer des sols en fonction des risques de transfert du Cd du sol vers une culture. Par rapport à l’évolution du contexte réglementaire, le modèle statistique prédictif de la teneur en Cd dans le grain a montré par validation croisée qu’il pourrait discerner de façon assez fiable (88 %) des différences de 0.05 mg Cd.kg-1 de grain et que sa fiabilité serait moindre (65 %) pour des différences de 0.025 mg Cd.kg-1. / Cadmium (Cd) is a trace element found in agricultural soils which can contaminate the food chain by being taken up by plants and accumulated in consumed plant products. The bioavailability of Cd is a concept at the centre of the risk assessment of Cd transfer from soil to plants. Plants, taking up essentially the free form of Cd (Cd2+) in the soil solution, bioavailability is a function of two main processes, the Cd speciation in solution (the different chemical forms taken by the Cd in solution) and the partitioning of Cd2+ between the solid phase and the solution. The main objective of this work was to develop simple predictive operational models of Cd2+ concentrations in agricultural soil solution, by modelling either Cd speciation in soil solution or Cd2+ solid-solution partitioning, the latter to further inform the ability of the phase to replenish the soil solution during root absorption. We also looked for models for the prediction of Cd2+ levels found in durum wheat grains. We have developed two modelling approaches. The first, statistical, allows to produce simple models for operational purposes. The second, geochemical, allows to understand the dominant mechanisms and thus to judge the coherence of simple statistical models to represent complex physicochemical processes. These two approaches have consistently shown that for poorly contaminated agricultural soils, the exchanged Cd between the solid phase and the solution is likely to be weakly sorbed and can be estimated by the Cd extracted by 1M NH4NO3 minus a fraction attached to amorphous manganese oxides. Modelling also showed the importance of pH and Ca content in solution as variables controlling the solubility of Cd2+, probably because of their role in controlling the sorption site availability and Cd complexation. The best-performing statistical model for predicting Cd content in durum wheat also picks up these variables, suggesting that simple statistical models for speciation in solution and soil-solution partitioning of Cd are relevant models to estimate bioavailability and that they can be used to classify soils according to the risks of the transfer of soil Cd to a crop. Compared to the evolution of the regulatory context, the statistical model predictive of the Cd content in the grain shown by cross validation that it could discern relatively reliably (88%) the differences of 0.05 mg Cd.kg-1 of grain and that its reliability would be less (65%) for differences of 0.025 mg Cd.kg-1.

Afin de mieux comprendre les mécanismes du trafic cellulaire, les processus de transport des substrats vacuolaires à travers le tonoplaste, le stockage des métabolites et leur dégradation, une analyse globale et exhaustive du protéome vacuolaire d'Arabidopsis thaliana a été réalisée. La connaissance de la localisation subcellulaire des protéines permet de mieux comprendre la fonction des organelles et la compartimentation du métabolisme des plantes. Mais la description précise du protéome d'un organite nécessite d'identifier clairement les véritables protéines résidantes du compartiment étudié. Une tâche si précise est complexe puisqu'elle nécessite la mise en place d'une préparation d'organites purs et homogènes. Pour y parvenir, un protocole de purification de vacuoles à partir de protoplastes isolés de cellules en culture sur un gradient de densité de Ficoll a été amélioré. La combinaison de plusieurs approches de protéomique a permis d'identifier les protéines présentes dans les fractions vacuolaires soluble et membranaire de façon quantitative et fonctionnelle. Les différentes approches ont ainsi mis en évidence des associations et mécanismes moléculaires complexes qui régissent les différentes activités vacuolaires. Cette protéothèque de référence constitue une base pour étudier la dynamique du protéome vacuolaire en réponse à plusieurs stress incluant les métaux lourds. Plusieurs méthodes sans a priori et ciblée ont été proposé afin d'étudier l'impact du cadmium sur la vacuole, ce compartiment cellulaire clé de la détoxication. / To better understand the mechanisms governing cellular traffic, transport process of substrates across the tonoplast, storage of various metabolites and their ultimate degradation, a comprehensive and thorough analysis of Arabidopsis thaliana vacuolar proteome was performed. Protein subcellular localization knowledge is an important step toward assigning functions of organelles and plant metabolism compartmentation. But confident description of proteome organelle content requires clear identification of the true resident proteins of the studied compartment. This task involves pitfalls and requires that either organelle preparations are free of contaminants or that techniques are used to discriminate between genuine organelle residents and contaminating proteins. To achieve this, vacuoles purification protocol from protoplasts on a Ficoll density gradient has been improved. The combination of several proteomic approaches attempt to present soluble and membrane vacuolar proteins in a quantitative and functional manner. Different approaches have thus shown associations and complex molecular mechanisms that govern the various vacuolar activities. The constitute proteins library provides references to study the vacuolar proteome dynamics in response to different stresses including heavy metals. Many methods without a priori or targeted were proposed to study the impact of cadmium on the vacuole, the key cell compartment of detoxification. Proteomics provides powerful tools for characterizing the protein contents of vacuoles during cadmium stress.

La protéine « Selenium Binding Protein » (SBP1), présente chez la plupart des êtres vivants, a un rôle qui n'est pas encore élucidé. Cette protéine possède dans sa structure primaire de nombreux sites potentiels de liaisons aux métaux. Chez Arabidopsis thaliana, la surexpression de SBP1 augmente la tolérance à deux composés toxiques pour la plante, le cadmium (Cd) et le sélénium (Se) qui sont présents dans les sols pollués. Pour mieux comprendre la fonction de SBP1 dans les mécanismes de détoxication, une démarche intégrée combinant deux approches complémentaires, in vitro et in planta, a été menée. La caractérisation biochimique de SBP1 a mis en évidence ses propriétés chélatrices vis-à-vis de différents ligands dont le Cd et le Se. Le Cd se lie à SBP1 avec un ratio molaire ligand/SBP1 de 3 et un KD de 2,2 × 10-7 M via principalement des acides aminés soufrés et potentiellement à moindre échelle des résidus histidines. Le Se, initialement sous forme SeO32-, se lie à SBP1 de façon covalente, avec un ratio molaire ligand/SBP1 de 1, via les cystéines 21 et 22 pour former une liaison de type R-S-Se-S-R. Les analyses in planta de localisation subcellulaire ont montré que SBP1 était à la fois cytosolique et nucléaire. L'utilisation de lignées bioluminescentes a permis d'analyser la zone promotrice du gène SBP1. Le motif cis ‘GAGAC' connu pour être impliqué dans la régulation de certains gènes à une carence en soufre (S) a été identifié comme élément cis majeur de la régulation de l'expression de SBP1 en réponse à différents stress, dont le Cd et le Se. Ce résultat démontre l'existence d'un lien entre la fonction de SBP1 et une demande en S de la cellule. La surexpression de SBP1 in planta perturbe le niveau d'accumulation du Se dans les parties aériennes, mais pas sa spéciation. L'ensemble de ces résultats semble indiquer que SBP1 soit impliquée dans des mécanismes de détoxication via ses propriétés chélatrices et qu'elle joue également un rôle dans le métabolisme du S et du Se. / The function of the protein “Selenium binding protein 1” (SBPP1), present in almost all organisms, is not yet well established. This protein has numerous potential metal binding sites. In Arabidopsis thaliana, SBP1 overexpression increases tolerance to two toxic compounds for the plant, cadmium (Cd) and selenium (Se), which are often found as soil pollutants. For a better understanding of SBP1 function and its involvement in detoxification mechanisms, an integrated approach combining in vitro and in planta experiments, has been performed. Biochemical characterization of SBP1 has revealed its chelating properties to different ligands including Cd and Se. Cd is bound to SBP1 with a metal ion to protein molar ratio of 3 and a KD of 2.2 × 10-7 M mainly via sulfur-containing amino acids and potentially histidine residues. Se from SeO32- can covalently bound SBP1 with a ligand to protein molar ratio of 1. This binding occurs via cysteines 21 and 22 and forms a R-S-Se-S-R complex. In planta analyses have shown that SBP1 is cytosolic and nuclear. The use of bioluminescent lines allowed the identification of a GAGAC motif in the SBP1 promoter region. This motif is a sulfur starvation responsive element and a major cis element involved in SBP1 expression in response to stress, including Cd and Se. The result directly links SBP1 function to an enhanced sulfur demand of the cell. SBP1 over expression in plants disturbs Se accumulation in shoots but not its speciation. All together these results strongly suggested that SBP1 could act as a detoxifying protein through its chelating properties and plays a role in S/Se metabolisms.

abstract: The energy band gap of a semiconductor material critically influences the operating wavelength of an optoelectronic device. Realization of any desired band gap, or even spatially graded band gaps, is important for applications such as lasers, light-emitting diodes (LEDs), solar cells, and detectors. Compared to thin films, nanowires offer greater flexibility for achieving a variety of alloy compositions. Furthermore, the nanowire geometry permits simultaneous incorporation of a wide range of compositions on a single substrate. Such controllable alloy composition variation can be realized either within an individual nanowire or between distinct nanowires across a substrate. This dissertation explores the control of spatial composition variation in ternary alloy nanowires. Nanowires were grown by the vapor-liquid-solid (VLS) mechanism using chemical vapor deposition (CVD). The gas-phase supersaturation was considered in order to optimize the deposition morphology. Composition and structure were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive x-ray spectroscopy (EDS), and x-ray diffraction (XRD). Optical properties were investigated through photoluminescence (PL) measurements. The chalcogenides selected as alloy endpoints were lead sulfide (PbS), cadmium sulfide (CdS), and cadmium selenide (CdSe). Three growth modes of PbS were identified, which included contributions from spontaneously generated catalyst. The resulting wires were found capable of lasing with wavelengths over 4000 nm, representing the longest known wavelength from a sub-wavelength wire. For CdxPb1-xS nanowires, it was established that the cooling process significantly affects the alloy composition and structure. Quenching was critical to retain metastable alloys with x up to 0.14, representing a new composition in nanowire form. Alternatively, gradual cooling caused phase segregation, which created heterostructures with light emission in both the visible and mid-infrared regimes. The CdSSe alloy system was fully explored for spatial composition variation. CdSxSe1-x nanowires were grown with composition variation across the substrate. Subsequent contact printing preserved the designed composition gradient and led to the demonstration of a variable wavelength photodetector device. CdSSe axial heterostructure nanowires were also achieved. The growth process involved many variables, including a deliberate and controllable change in substrate temperature. As a result, both red and green light emission was detected from single nanowires. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2012