Les MOSFETs ultra-thin body UTB ont été fabriqués avec une technologie auto-alignée. Le canal conducteur est constitué d’InGaAs à 75% de taux d’indium ou d’un composite InAs/In0,53Ga0,47As. Une fine couche d'InP (3 nm) a été insérée entre le canal et l'oxyde, afin d’éloigner les défauts de l’interface oxyde-semiconducteur du canal. Enfin, une épaisseur de 4 nm d'oxyde de grille (Al2O3) a été déposée par la technique de dépôt des couches atomiques. Les contacts ohmiques impactent les performances des MOSFETs. La technologie UTB permet difficilement d’obtenir des contacts S/D de faibles résistances. De plus, l’utilisation de la technique d’implantation ionique pour les architectures UTB est incompatible avec le faible budget thermique des matériaux III-V et ne permet pas d’obtenir des contacts ohmiques de bonne qualité. Par conséquent, nous avons développé une technologie auto-alignée, basée sur la diffusion du Nickel « silicide-like » par capillarité à basse température de recuit (250°C) pour la définition des contacts de S/D. Finalement, nous avons étudié et analysé la résistance de l'alliage entre le Nickel et les III-V. A partir de cette technologie, des MOSFET In0,75Ga0,25As et InAs/In0,53Ga0,47As ont été fabriqués. On constate peu de différences sur les performances électriques de ces deux composants. Pour le MOSFET InAs/InGaAs ayant une longueur de grille LG =150 nm, un courant maximal de drain ID=730 mA/mm, et une transconductance extrinsèque maximale GM, MAX = 500 mS/mm ont été obtenu. Le dispositif fabriqué présente une fréquence de coupure fT égale à 100 GHz, et une fréquence d'oscillation maximale fmax de 60 GHz, pour la tension drain-source de 0,7 V. / The UTB MOSFETs were fabricated by self-aligned method. Two thin body conduction channels were explored, In0,75Ga0,25As and a composite InAs/ In0,53Ga0,47As. A thin upper barrier layer consisting of InP (3nm) is inserted between the channel and the oxide layers to realized a buried channel. Finally, the Al2O3 (4 nm) was deposited by the atomic layer deposition (ALD) technique. It is well known that the source and drain (S/D) contact resistances of InAs MOSFETs influence the devices performances. Therefore, in our ultra-thin body (UTB) InAs MOSFETs design, we have engineered the contacts to achieve good ohmic contact resistances. Indeed, for this UTB architecture the use of ion implantation technique is incompatible with a low thermal budget and cannot allow to obtain low resistive contacts. To overcome this limitation, an adapted technological approach to define ohmic contacts is presented. To that end, we chose low thermal budget (250°C) silicide-like technology based on Nickel metal. Finally, we have studied and analyzed the resistance of the alloy between Nickel and III-V (Rsheet). MOSFET with two different epilayer structures (In0,75Ga0,25As and a composite InAs/ In0,53Ga0,47As) were fabricated with a gate length (LG) of 150 nm. There were few difference of electrical performance of these two devices. We obtained a maximum drain current (ION) of 730 mA/mm, and the extrinsic transconductance (GM, MAX) showed a peak value of 500 mS/mm. The devices exhibited a current gain cutoff frequency fT of 100 GHz and maximum oscillation frequency fmax of 60 GHz for drain to source voltage (VDS) of 0.7 V.

The goals of this project are study Cu free back contact alternatives for CdS/CdTe thin film solar cells, and to research dry etching for CdTe surface preparation before contact application. In addition, an attempt has been made to evaluate the stability of some of the contacts researched. The contacts studied in this work include ZnTe/Cu2Te, Sb2Te3, and Ni-P alloys. The ZnTe/Cu2Te contact system is studied as basically an extension of the earlier work done on Cu2Te at USF. RF sputtering from a compound target of ZnTe and Cu2Te respectively deposits these layers on etched CdTe surface. The effect of Cu2Te thickness and deposition temperature on contact and cell performance will be studied with the ZnTe depositions conditions kept constant. C-V measurements to study the effect of contact deposition conditions on CdTe doping will also be performed. These contacts will then be stressed to high temperatures (70-100 degrees C) and their stability with stress time is analyzed. Sb2Te3 will be deposited on glass using RF sputtering, to study film properties with deposition temperature. The Sb2Te3 contact performance will also be studied as a function of the Sb2Te3 deposition temperature and thickness. The suitability of Ni-P alloys for back contacts to CdTe solar cells was studied by forming a colloidal mixture of Ni2P in graphite paste. The Ni-P contacts, painted on Br-methanol etched CdTe surface, will be studied as a function of Ni-P concentration (in the graphite paste), annealing temperature and time. Some of these cells will undergo temperature stress testing to determine contact behavior with time. Dry etching of CdTe will be studied as an alternative for wet etching processes currently used for CdTe solar cells. The CdTe surface is isotropically etched in a barrel reactor in N2, Ar or Ar:O2 ambient. The effect of etching ambient, pressure, plasma power and etch time on contact performance will be studied.

Tesis (mag?ster en derecho de familia(s), derecho de la infancia y la adolescencia) / Actividad Formativa Equivalente a Tesis (AFET)

As a global climate phenomenon, the El Ni??o-Southern Oscillation (ENSO) involves the coupling of the ocean and the atmosphere. Most climate prediction studies have, by far, only investigated the teleconnections between global climatic anomalies and the ???surface??? predictors of ENSO. The prediction models resulting from these studies have generally suffered from inadequate, if not the lack of, skill across the so-called boreal ???spring barrier???. This is illustrated in the first part of this thesis where the applicability of the SOI phase for long-lead rainfall projections in Australia is discussed. With the increasing availability of subsurface ocean temperature data, the characteristics of the Pacific Ocean???s heat content and its role in ENSO are now better understood. The second part of this thesis investigated the predictability of ENSO using the thermocline as a predictor. While the persistence and SST-based ENSO hindcasts dropped in skill across the spring barrier, the thermocline-based hindcasts remained skillful even up to a lag of eighteen months. Continuing on the favorable results of ENSO prediction, the third part of this thesis extended the use of the thermocline in the prediction of Australia???s rainfall and streamflow. When compared to models that use ???surface??? predictors, the model that incorporated thermocline information resulted in more skillful projections of rainfall and streamflow especially at long lead-times. More importantly, significant increases in skill of autumn and winter projections demonstrate the ability of the subsurface ocean to retain some climatic memory across the predictability barrier. This resilience can be attributed to the high persistence of the ocean heat content during the first half of the year. Based on weighting, the model averaging exercise also affirmed the superiority of the ???subsurface??? model over the ???surface??? models in terms of streamflow projections. The encouraging findings of this study could have far-reaching implications not only to the science of ENSO prediction but also to the more pragmatic realm of hydrologic forecasting. What this study has demonstrated is an alternative predictor that is suitable for the long range forecasting of ENSO, rainfall and streamflow. With better hydrologic forecasting comes significant improvement in the management of reservoirs which eventually leads to an increase in the reliability and sufficiency of water supply provision.

Ce travail est consacré à l'étude de l'ingénierie des joints de grains dans les superalliages à base de Nickel pour disques de turbines aéronautiques. L'ingénierie des joints de grains a montré son efficacité dans l'amélioration des propriétés en fatigue et en fluage dans certains alliages de cuivre et de nickel. Cette amélioration est obtenue en réalisant une succession de déformations à température ambiante séparées par des traitement thermiques. Ce traitement a pour objectif de modifier la distribution du réseau de joints de grains. L'objectif de l'étude est d'adapter ces traitements au procédé du forgeage à haute température des superalliages. Une étude expérimentale est menée pour mettre en évidence l'influence des paramètres de forgeage sur les caractéristiques du réseau de joints de grains. La caractérisation de ce réseau est faite grâce à la réalisation de cartographies d'orientations cristallographiques par EBSD. Une méthode de caractérisation innovante basée sur la discrétisation des cartographies en réseaux de points triples est proposée. Cette méthode permet d'analyser la connectivité du réseau de joints de grains en vue d'une corrélation avec les propriétés mécaniques.

Les travaux présentés dans ce manuscrit ont permis dans un premier temps de développer avec succès deux nouvelles méthodes pour réaliser des cyclisations radicalaires 5-endo et dans un second temps d'illustrer le potentiel synthétique de la chimie radicalaire des xanthates, mise au point au sein du laboratoire, par son application à la synthèse de substances biologiquement actives. Dans la première partie, différentes approches permettant un accès aux γ-lactames par cyclisation radicalaire 5-endo sans l'utilisation de métaux lourds toxiques tel que l'hydrure de tributylétain ont été étudiées. L'originalité des deux systèmes développés réside dans l'oxydation du radical issu de la cyclisation. Ainsi, contrairement aux réactions induites par l'hydrure de tributylétain, différents γ-lactames insaturés peuvent être obtenus après déprotonation. Les travaux réalisés dans la deuxième partie ont permis l'élaboration de nombreux analogues des duocarmycines, qui ont fait l'objet de tests biologiques. Ces différents composés ont pu être préparés grâce à une synthèse convergente et efficace qui consiste à coupler un noyau alkylant avec un bras intercalant par formation d'une hydrazone. Différentes parties alkylantes ont été synthétisées rapidement grâce à l'application de la séquence d'addition-cyclisation radicalaire à partir de xanthate, précédemment développée au laboratoire. Une étude a également été menée pour tenter d'apporter des modifications à ces molécules. Enfin, nous avons préparé divers bras intercalants selon plusieurs méthodes. Nous avons ensuite couplé les différentes parties. Les molécules ainsi synthétisées ont révélé des activités cytotoxiques très prometteuses (IC50 ~ 0.5-1.2 µM). Cette étude prouve donc l'intérêt synthétique de la chimie radicalaire des xanthates.

<p>In this thesis the magnetic and structural properties of ultra-thin 3d transition metals films have been investigated, in particular Fe, Ni and Co films. X-ray Magnetic Circular Dichroism (XMCD) has provided element specific spin (m_s ) and orbital (m_l ) moments per atom by utilizing the magneto optic sum-rules. Element specific hysteresis curves have been measured by means of X-ray Resonant Magnetic Scattering (XRMS), and the local crystallographic structure has been investigated using Extended X-ray Absorption Fine Structure (EXAFS). </p><p>By performing XMCD on Fe/Ag(100) we observe a spin reorientation from in-plane to out-of-plane as the Fe thickness is lowered. At temperatures below 300K it occurs around 5-7 mono layers (ML) of Fe. While reorienting the magnetization out-of-plane the orbital moment increases with 125% but only a minor increase (5%) of the spin moment is observed. Extended X-ray Absorption Fine Structure (EXAFS) measurements indicate that films 6 ML and thicker have a bulk-like bcc structure. For the thin out-of-plane films, the local crystallographic structure is more complicated. </p><p>The spin reorientation of the Au/Co/Au tri-layer system has been studied as a function of temperature, Co layer and Au cap thickness. An unexpected behavior of the orbital moment upon spin reorientation is found in these systems. An ex-situ prepared sample shows a smooth spin reorientation from an in-plane to an out-of-plane easy magnetization direction as the temperature is lowered from 300K to 200K. In-situ prepared samples have also been investigated and a novel phase diagram has been identified. The Au/Co interface has been explored during the Au capping by means of photoemission measurements. </p><p>In the bi- and tri-layer system of Fe and Ni we have been able to manipulate the spin reorientation by varying the Fe and Ni thickness. A novel non-collinear interlayer exchange interaction for 3d ferro magnets in direct contact has been discovered for a set of samples. This exchange interaction is found to be strongly dependant on the preparation conditions.</p>

Dynamic Mechanical Analyzer (DMA) was used to study the frequency dependence of storage and loss modulus of amorphous Pd₄₀Ni₁₀Cu₃₀P₂₀ alloy over a broad frequency range around its glass transition temperature. The amorphous samples were subjected to two testing conditions: constant frequency with continuous heating and isothermal with frequency sweep. The storage modulus E′ exhibited a sigmoidal change from about 90 GPa to a low value of about 0 GPa over the glass transition region. The loss modulus, E″, was characterized by an asymmetrical peak with a smaller slope at the low temperature side than at the high temperature side upon heating. These changes in moduli were associated with mechanical relaxation due to atomic motion. Similar results were also obtained under isothermal condition. The Kohrausch-Williams-Watts function was used to fit the data obtained under the isothermal condition. The peak frequencies obtained were then fitted to the VFT equation and the scaling law equation. / Singapore-MIT Alliance (SMA)

We report on the process parameters of nanoimprint lithography (NIL) for the fabrication of two-dimensional (2-D) photonic crystals. The nickel mould with 2-D photonic crystal patterns covering the area up to 20mm² is produced by electron-beam lithography (EBL) and electroplating. Periodic pillars as high as 200nm to 250nm are produced on the mould with the diameters ranging from 180nm to 400nm. The mould is employed for nanoimprinting on the poly-methyl-methacrylate (PMMA) layer spin-coated on the silicon substrate. Periodic air holes are formed in PMMA above its glass-transition temperature and the patterns on the mould are well transferred. This nanometer-size structure provided by NIL is subjective to further pattern transfer. / Singapore-MIT Alliance (SMA)

The Ni-Fe-S C-cluster of carbon monoxide dehydrogenases (CODH), which catalyzes the reversible oxidation of CO to CO2, can be stabilized in four redox states: Cox, Cred1, Cint, and Cred2. The best-supported mechanism of catalysis involves a one-electron reductive activation of Cox to Cred1 and a catalytic cycle in which Cred1 binds and oxidizes CO, forming Cred2 and releasing CO2. Recently reported experiments appear to have disqualified this mechanism, as activation was concluded to require reduction to a C-cluster state more reduced than Cred1. The results presented in this dissertation suggest that the activation potential was milder than that required to reduce these clusters. The results support a mechanism in which Cred1 is the form of the cluster that reacts with CO. The structure of the active-site C-cluster in CO dehydrogenase from Carboxydothermus hydrogenoformans (CODHCh) includes a ??2-sulfide ion bridged to the Ni and unique Fe, while the same cluster in enzymes from Rhodospirillum rubrum (CODHRr) and Moorella thermoacetica (CODHMt) lack this ion. This difference was investigated by exploring effects of sulfide on activity and spectral properties. Sulfide partially inhibited CO oxidation activities of CODHRr and CODHMt. Adding sulfide to CODHMt in the Cred1 state caused the gav = 1.82 Electron Paramagnetic Resonance spectroscopy (EPR) signal to decline and new features to appear. Sulfide did not affect the gav = 1.86 signal from the Cred2 state. A model was developed in which sulfide binds reversibly to Cred1, inhibiting catalysis. The results also suggest that the substrate hydroxyl group bridges the Ni and unique Fe. A cysteine residue recently found to form a persulfide bond with the C-cluster was characterized. The Ser mutant of the persulfide-forming Cys316 was inactive and displayed no C-cluster EPR signals. Electronic absorption and metal analysis suggest that the C-cluster is absent in this mutant. The persulfide bond appears to be essential for either the assembly or stability of the C-cluster, and/or for eliciting the redox chemistry of the C-cluster required for catalytic activity.