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Ces dernières années, les nanocristaux (NCs) semi-conducteurs ont reçu un intérêt grandissant pour deux raisons principalement. D'une part, ces objets possèdent des tailles qui se situent entre celles des molécules et des matériaux cristallins. Leur étude d'un point de vue fondamental est par conséquent utile pour mieux comprendre les propriétés de la matière condensée en fonction de la dimension des objets étudiés . En particulier, les NCs de chalcogénures de plomb possèdent une constante diélectrique élevée (ε∞=23 pour PbSe) et des porteurs de charges ayant des faibles masses effectives, conduisant à la formation d'excitons avec un large rayon de Bohr effectif. De ce fait, ce sont des objets de choix pour étudier le régime de fort confinement quantique. D'autre part, la miniaturisation des composants électroniques nécessite l'utilisation d'objets semi-conducteurs aux dimensions de plus en plus petites, avec des coûts de fabrication les plus bas possibles. Les NCS semi-conducteurs, dont les synthèses chimiques sont généralement simples, répondent à cet enjeu et un certain nombre d'applications tirent avantage de leurs propriétés optiques. Dans la première partie de cette thèse, la méthode de synthèse des NCs de PbSe est décrite. Grâce à l'utilisation de plusieurs techniques de caractérisation (microscopies électroniques, diffraction des rayons X (XRD), diffraction électronique (SAED)), l'optimisation de cette méthode a conduit à l'obtention de NCs monodisperses en taille et possédant une structure cristalline parfaite. Dans un second temps, des études plus fines en spectroscopie Raman ont confirmé la qualité structurale des NCs. Elles ont aussi permis d'étudier les effets de confinement sur le spectre des phonons optiques longitudinaux. Enfin, les NCs de PbSe se détériorant rapidement à l'air, des structures coeur coquille ont été élaborées pour réaliser de l'ingénierie de bande dans des NCs à hétérostructures. En utilisant le rayonnement synchrotron et après avoir développé des techniques de dépôt de films ultra minces de NCs coeur-coquille PbSe/CdSe, la discontinuité de la bande de valence de ces structures a été étudiée par spectroscopie de photoélectrons.

This thesis reports a passive method for Fermi level regulation in quantum dot assemblies through ground state transfer between QDs. Here, ZnTe/CdS, and PbSe/CdSe core/shell QDs were used as valence band electron donors, while Cu containing CdS or ZnSe acts as electron acceptor QDs. Prior to study of ground state charge transfer process, this report discusses the synthesis of ZnTe/CdS, and PbSe/CdSe core shell QDs, which are later used to study charge transfer. Since ZnTe QDs are unstable and prone to oxidation, a CdS coated ZnTe QDs were used. Growing a CdS shell on ZnTe core is difficult because high reduction potential of Te. To overcome this problem, partially reduced sulphur is used for the synthesis of ZnTe/CdS. The peculiar optical properties exhibited by ZnTe/CdS also have been discussed. Even though the synthesis of Lead chalcogenide nanoparticles has been investigated previously, certain inconsistencies between the behavior expected from known mechanisms and empirical observations. An anion exchange mechanism is proposed and demonstrated to be involved in PbSe formation. Both ZnTe and PbSe based QDs are extensively used to study hole injection and copper containing QDs were used as acceptors. The charge transfer has been studied using optical spectroscopy. The structure and composition of the assemblies was identified using powder crystallography, electron-microscopy and composition analysis. The unique physical and chemical properties of these materials are exciting both fundamentally as well as from the point of view of applications.

Indiana University-Purdue University Indianapolis (IUPUI) / Mass customization, small lot sizes, reduced cost, high variability of product types and changing product portfolio are characteristics of modern manufacturing systems during life cycle. A direct consequence of these characteristics is a more complex system and supply chain. Product lifecycle management (PLM) and model based system engineering (MBSE) are tools which have been proposed and implemented to address different aspects of this complexity and resulting challenges. Our previous work has successfully implemented a MBSE model into a PLM platform. More specifically, Pattern based system engineering (S* pattern) models of systems are integrated with TEAMCENTER to link and interface system level with component level, and streamline the lifecycle across disciplines. The benefit of the implementation is two folded. On one side it helps system engineers using system engineering models enable a shift from learning how to model to implementing the model, which leads to more effective systems definition, design, integration and testing. On the other side the PLM platform provides a reliable database to store legacy data for future use also track changes during the entire process, including one of the most important tools that a systems engineer needs which is an automatic report generation tool. In the current work, we have configured a PLM platform (TEAMCENTER) to support automatic generation of reports and requirements tables using a generic Oil Filter system lifecycle. There are three tables that have been configured for automatic generation which are Feature definitions table, Detail Requirements table and Stakeholder Feature Attributes table. These tables where specifically chosen as they describe all the requirements of the system and cover all physical behaviours the oil filter system shall exhibit during its physical interactions with external systems. The requirement tables represent core content for a typical systems engineering report. With the help of the automatic report generation tool, it is possible to prepare the entire report within one single system, the PLM system, to ensure a single reliable data source for an organization. Automatic generation of these contents can save the systems engineers time, avoid duplicated work and human errors in report preparation, train future generation of workforce in the lifecycle all the while encouraging standardized documents in an organization.

No description available.

De nos jours la plupart des organisations pour ne pas dire toutes, dépendent des technologies de l'information et de la communication (TIC) pour supporter plusieurs tâches et processus (quelquefois critiques). Cependant, dans la plupart des cas, les organisations et en particulier les petites entreprises accordent une importance limitée à l'information et à sa sécurité. En outre, sécuriser de tels systèmes est une tâche difficile en raison de la complexité et de la connectivité croissante du matériel et du logiciel dans le développement des TICs. Cet aspect doit alors être pris en compte dès les premières phases de conception. Dans ce travail, nous proposons une approche basée sur les modèles permettant de sécuriser des architectures logicielles en utilisant des patrons. Les contributions de ce travail sont : (1) un cadre de conception intégré pour la spécification et l'analyse d'architectures logicielles sécurisées, (2) une nouvelle méthodologie à base de modèles et de patrons et (3) une suite d'outils. Le fondement de l'approche associe un environnement basé sur des langages de modélisation pour la spécification et l'analyse des modèles d'architectures sécurisées et un dépôt à base de modèles d'artéfacts dédiés à la sécurité (modèle de patrons de sécurité, menaces et propriétés de sécurités) permettant la réutilisation de savoir-faire et de connaissances capitalisées. Pour cela on utilise des langages de modélisation pour la spécification et l'analyse de l'architecture. Le processus associé est constitué des activités suivantes : (a) analyse de risques à base de modèle appliquée à l'architecture du système pour identifier des menaces, (b) sélection et importation de modèles de patrons de sécurité, afin d'arrêter ou de mitiger les menaces identifiées, vers l'environnement de modélisation cible, (c) intégration de modèles de patrons dans le modèle d'architecture, (d) analyse de l'architecture obtenue par rapports aux exigences non-fonctionnelles et aux menaces résiduelles. Dans ce cadre, on s'est focalisé sur la vérification du maintien du respect des contraintes temporelles après application des patrons. La recherche de menaces résiduelles est réalisée à l'aide de techniques de vérification exploitant une représentation formelle des scénarios de menaces issus du modèle STRIDE et basés sur des référentiels de menaces existants (ex., CAPEC). Dans le cadre de l'assistance pour le développement des architectures sécurisées, nous avons implémenté une suite structurée d'outils autour du framework SEMCO et de la plateforme Eclipse Papyrus pour supporter les différentes activités basées sur un ensemble de langages de modélisation conforme à des standards OMG (UML et ses profils). Les solutions proposées ont été évaluées à travers l'utilisation d'un cas d'étude autour des systèmes SCADA (systèmes de contrôle et d'acquisition de données). / Nowadays most organizations depend on Information and Communication Technologies (ICT) to perform their daily tasks (sometimes highly critical). However, in most cases, organizations and particularly small ones place limited value on information and its security. In the same time, achieving security in such systems is a difficult task because of the increasing complexity and connectivity in ICT development. In addition, security has impacts on many attributes such as openness, safety and usability. Thus, security becomes a very important aspect that should be considered in early phases of development. In this work, we propose an approach in order to secure ICT software architectures during their development by considering the aforementioned issues. The contributions of this work are threefold: (1) an integrated design framework for the specification and analysis of secure software architectures, (2) a novel model- and pattern-based methodology and (3) a set of supporting tools. The approach associates a modeling environment based on a set of modeling languages for specifying and analyzing architecture models and a reuse model repository of modeling artifacts (security pattern, threat and security property models) which allows reuse of capitalized security related know-how. The approach consists of the following steps: (a) model-based risk assessment performed on the architecture to identify threats, (b) selection and instantiation of security pattern models towards the modeling environment for stopping or mitigating the identified threats, (c) integration of security pattern models into the architecture model, (d) analysis of the produced architecture model with regards to other non-functional requirements and residual threats. In this context, we focus on real-time constraints satisfaction preservation after application of security patterns. Enumerating the residual threats is done by checking techniques over the architecture against formalized threat scenarios from the STRIDE model and based on existing threat references (e.g., CAPEC). As part of the assistance for the development of secure architectures, we have implemented a tool chain based on SEMCO and Eclipse Papyrus to support the different activities based on a set of modeling languages compliant with OMG standards (UML and its profiles). The assessment of our work is presented via a SCADA system (Supervisory Control And Data Acquisition) case study.

>Magister Scientiae - MSc / In this study PbSe quantum dots (QDs) were successfully synthesized via the organometallic and aqueous routes. Optical characterization was carried out using photoluminescence (PL) spectroscopy, structural and morphological characterization were carried out using X-ray diffraction (XRD) and transmission electron microscopy (TEM). Energy-dispersive X-ray spectroscopy (EDS) was used to determine the composition of the QDs. All the synthesized QDs were found to have emissions within the near-infrared region of the spectrum (≥1000 nm) with most of them being less than 5 nm in size. The aqueous synthesized QDs had a perfect Gaussian emission spectrum with a FWHM of ~23 nm indicating pure band gap emission and narrow size distribution respectively. The QDs were determined to have a cubic rock-salt crystal structure consistent with bulk PbSe. The aqueous synthesized QDs were however not stable in solution with the QDs precipitating after approximately 48 h. The organometallic synthesized QDs were transferred into the aqueous phase by exchanging the surface oleic acid ligands with 11-mercaptoundecanoic acid ligands. The ligand exchanged QDs were however stable in solution for over two weeks. The effects of reaction parameters on the optical and structural properties of the organometallic synthesized QDs were investigated by varying the reaction time, temperature, ligand purity, lead and selenium sources. It was observed that larger QDs were formed with longer reaction times, with reactions proceeding faster at higher reaction temperatures than at lower temperatures. Varying the ligand purity was found to have minimal effects on the properties of the synthesized QDs. The lead and selenium sources contributed largely to the properties of the QDs with lead oxide producing spherical QDs which were smaller compared to the cubic QDs produced from lead acetate. TBPSe was seen to produce smaller QDs as compared to TOPSe. The cytotoxity of the synthesized QDs was determined following the WST-1 cell viability assay with the QDs being found to be non-toxic at all the tested concentrations

<div>Inorganic metal chalcogenide materials are of great importance in the semiconducting field for various electronic applications such as photovoltaics, thermoelectrics, sensors, and many others. Compared to traditional vacuum processing routes, solution processing provides an alternate cost-effective route to synthesize these inorganic materials through its ease of synthesis and device fabrication, higher material utilization, mild processing conditions, and opportunity for roll-to-roll manufacturing. One such versatile solution chemistry involving a mixture of amine and thiol species has evolved in the past few years as a common solvent for various precursor dissolutions including metal salts, metal oxides, elemental metals, and chalcogens.</div><div><br></div><div>The amine-thiol solvent system has been used by various researchers for the fabrication of inorganic materials, but without the complete understanding of the chemistry involved in this system, utilizing its full potential, and overcoming any inherent limitations will be difficult. So, to identify the organometallic complexes and their reaction pathways, the precursor dissolutions in amine-thiol solutions, specifically for elemental metals like Cu, In and chalcogens like Se, Te were studied using X-ray absorption, nuclear magnetic resonance, infrared, and Raman spectroscopy along with electrospray ionization mass spectrometry techniques. These analyses suggested the formation of metal thiolate complexes in the solution with the release of hydrogen gas in the case of metal dissolutions confirming irreversibility of the dissolution. Insights gained for chalcogen dissolutions confirmed the formation of different species like monoatomic or polyatomic clusters when different amine-thiol pair is used for dissolution. Results from these analyses also identified the role of each component in the dissolution which allowed for tuning of the solutions by isolating the complexes to reduce their reactivity and corrosivity for commercial applications.</div><div><br></div><div>After identifying complexes in metal dissolution for Cu and In metals, the decomposition pathway for these complexes was studied using X-ray diffraction and gas chromatography mass spectrometry techniques which confirmed the formation of phase pure metal chalcogenide material with a release of volatile byproducts like hydrogen sulfide and thiirane. This allowed for the fabrication of impurity-free thin-film Cu(In,Ga)S2 material for use in photovoltaic applications. The film fabrication with reduced carbon impurity achieved using this solvent system yielded a preliminary promising efficiency beyond 12% for heavy alkali-free, low bandgap CuInSe2 material. Along with promising devices, by utilizing the understanding of the chalcogen complexation, a new method for CuInSe2 film fabrication was developed with the addition of selenide precursors and elemental selenium which enabled first-ever fabrication of a solution-processed CuInSe2 thin film with thickness above 2 μm and absence of any secondary fine-grain layer.</div><div><br></div><div>Along with thin-film fabrication, a room temperature synthesis route for lead chalcogenide materials (PbS, PbSe, PbTe) with controlled size, shape, crystallinity, and composition of nanoparticle self-assemblies was demonstrated. Micro-assemblies formed via this route, especially the ones with hollow-core morphology were subjected to a solution-based anion and cation exchange to introduced desired foreign elements suitable for improving the thermoelectric properties of the material. Adopting from traditional hot injection and heat up synthesis routes, a versatile synthesis procedure for various binary, ternary, and quaternary metal chalcogenide (sulfide and sulfoselenide) nanoparticles from elemental metals like Cu, Zn, Sn, In, Ga, and Se was developed. This new synthesis avoids the incorporation of impurities like O, Cl, I, Br arising from a traditional metal oxide, halide, acetate, or other similar metal salt precursors giving an opportunity for truly impurity-free colloidal metal chalcogenide nanoparticle synthesis.</div>