This thesis presents a review of the theory of evaporation of pure substances with respect to kinetic and mechanistic models. These concepts are applied to multi-component evaporation and a model for the evaporation of solute atoms from a solvent is postulated. The evaporation experiments were performed on Fe 1% Mn melts at a constant pressure of approximately 10 microns over a temperature range of 1320° to 1810°C. The correlation between the experimental results and the expected theoretical results is discussed thoroughly in terms of surface control and diffusion control. / Thesis / Master of Engineering (ME)

A study of the condensation of hydrocarbons and zeotropic hydrocarbon mixtures in smooth horizontal tubes was conducted. Measurements of condensation heat transfer coefficients and frictional pressure drop were taken over a range of mass fluxes (G = 150 – 450 kg m-2 s-1), a range of reduced pressures (Pr = 0.25 - 0.95), for two tube diameters (D = 7.75 and 14.45 mm), several working fluid-to-coolant temperature differences (ΔTLM = 3 – 14°C) and temperature glides (ΔTGlide) between 7 - 14°C. The wide range of conditions investigated in this study provides considerable insight on the transport phenomena influencing condensation in pure fluids and their mixtures. The trends in heat transfer coefficient and frictional pressure gradient are discussed and compared with the predictions of correlations from the literature. The results of the experiments, combined with previous flow visualization studies on hydrocarbons, were used to develop physically consistent heat transfer and frictional pressure gradient models that are applicable to pure fluids and zeotropic mixtures. A framework was developed for zeotropic mixture condensation that recommends a specific modeling approach based on the observed trends in the heat transfer coefficient and the points of deviations from pure fluid trends. The documentation of the condensation heat transfer and pressure drop behavior of environmentally friendly refrigerants, and the development of accurate correlations, will facilitate their widespread introduction as a working fluid for refrigeration cycles. Furthermore, the accurate pure fluid models, which serve as a baseline case for zeotropic mixture modeling, yield more effective predictions of zeotropic mixture condensation, which will lead to increased efficiencies of chemical processing plants.

Nous étudions la distillation extractive continue de mélanges azéotropiques à temperature de bulle minimale avec un entraineur lourd (classe 1.0-1a) avec comme exemples les mélanges acétone-méthanol avec l’eau et DIPE-IPA avec le 2-méthoxyethanol. Le procédé inclut les colonnes de distillation extractive et de régénération de l’entraineur en boucle ouverte et en boucle fermée. Une première stratégie d’optimisation consiste à minimiser la fonction objectif OF en cherchant les valeurs optimales du débit d’entraineur FE, les positions des alimentations en entraineur et en mélange NFE, NFAB, NFReg, les taux de reflux R1, R2 et les débits de distillat de chaque colonne D1, D2. OF décrit la demande en énergie par quantité de distillat et tient compte des différences de prix entre les utilités chaudes et froides et entre les deux produits. La deuxième stratégie est une optimisation multiobjectif qui minimise OF, le coût total annualisé (TAC) et maximise deux nouveaux indicateurs thermodynamiques d’efficacité de séparation extractive totale Eext et par plateau eext. Ils décrivent la capacité de la section extractive à séparer le produit entre le haut et le bas de la section extractive. L’analyse thermodynamique des réseaux de courbes de résidu ternaires RCM et des courbes d’isovolatilité montre l’intérêt de réduire la pression opératoire dans la colonne extractive pour les séparations de mélanges 1.0-1a. Une pression réduite diminue la quantité minimale d’entraineur et accroît la volatilité relative du mélange binaire azéotropique dans la région d’opération de la colonne extractive. Cela permet d’utiliser un taux de reflux plus faible et diminue la demande énergétique. La première stratégie d’optimisation est conduite avec des contraintes sur la pureté des produits avec les algorithmes SQP dans les simulateurs Aspen Plus ou Prosim Plus en boucle ouverte. Les variables continues optimisées sont : R1, R2 et FE (étape 1). Une étude de sensibilité permet de trouver les valeurs de D1, D2 (étape 2) et NFE, NFAB, NFReg (étape 3), tandis l’étape 1 est faite pour chaque jeu de variables discrètes. Enfin le procédé est resimulé en boucle fermée et TAC, Eext et eext sont calculés (étape 4). Les bilans matières expliquent l’interdépendance des débits de distillats et des puretés des produits. Cette optimisation permet de concevoir des procédés avec des gains proches de 20% en énergie et en coût. Les nouveaux procédés montrent une amélioration des indicateurs Eext et eext. Afin d’évaluer l’influence de Eext et eext sur la solution optimale, la seconde optimisation multiobjectif est conduite. L’algorithme génétique est peu sensible à l’initialisation, permet d’optimiser les variables discrètes N1, N2 et utilise directement le shéma de procédé en boucle fermée. L’analyse du front de Pareto des solutions met en évidence l’effet de FE/F et R1 sur TAC et Eext. Il existe un Eext maximum (resp. R1 minimum) pour un R1 donné (resp. Eext). Il existe aussi un indicateur optimal Eext,opt pour le procédé optimal avec le plus faible TAC. Eext,opt ne peut pas être utilisé comme seule fonction objectif d’optimisation mais en complément des autres fonctions OF et TAC. L’analyse des réseaux de profils de composition extractive explique la frontière du front de Pareto et pourquoi Eext augmente lorsque FE diminue et R1 augmente, le tout en lien avec le nombre d’étage. Visant à réduire encore TAC et la demande énergétique nous étudions des procédés avec intégration énergétique double effet (TEHI) ou avec des pompes à chaleur (MHP). En TEHI, un nouveau schéma avec une intégration énergétique partielle PHI réduit le plus la demande énergétique. En MHP, la recompression partielle des vapeurs VRC et bottom flash partiel BF améliorent les performances de 60% et 40% respectivement. Au final, le procédé PHI est le moins coûteux tandis que la recompression totale des vapeurs est la moins énergivore. / We study the continuous extractive distillation of minimum boiling azeotropic mixtures with a heavy entrainer (class 1.0-1a) for the acetone-methanol with water and DIPE-IPA with 2-methoxyethanol systems. The process includes both the extractive and the regeneration columns in open loop flowsheet and closed loop flowsheet where the solvent is recycled to the first column. The first optimization strategy minimizes OF and seeks suitable values of the entrainer flowrate FE, entrainer and azeotrope feed locations NFE, NFAB, NFReg, reflux ratios R1, R2 and both distillates D1, D2. OF describes the energy demand at the reboiler and condenser in both columns per product flow rate. It accounts for the price differences in heating and cooling energy and in product sales. The second strategy relies upon the use of a multi-objective genetic algorithm that minimizes OF, total annualized cost (TAC) and maximizes two novel extractive thermodynamic efficiency indicators: total Eext and per tray eext. They describe the ability of the extractive section to discriminate the product between the top and to bottom of the extractive section. Thermodynamic insight from the analysis of the ternary RCM and isovolatility curves shows the benefit of lowering the operating pressure of the extractive column for 1.0-1a class separations. A lower pressure reduces the minimal amount of entrainer and increases the relative volatility of original azeotropic mixture for the composition in the distillation region where the extractive column operates, leading to the decrease of the minimal reflux ratio and energy consumption. The first optimization strategy is conducted in four steps under distillation purity specifications: Aspen Plus or Prosim Plus simulator built-in SQP method is used for the optimization of the continuous variables: R1, R2 and FE by minimizing OF in open loop flowsheet (step 1). Then, a sensitivity analysis is performed to find optimal values of D1, D2 (step 2) and NFE, NFAB, NFReg (step 3), while step 1 is done for each set of discrete variables. Finally the design is simulated in closed loop flowsheet, and we calculate TAC and Eext and eext (step 4). We also derive from mass balance the non-linear relationships between the two distillates and how they relate product purities and recoveries. The results show that double digit savings can be achieved over designs published in the literature thanks to the improving of Eext and eext. Then, we study the influence of the Eext and eext on the optimal solution, and we run the second multiobjective optimization strategy. The genetic algorithm is usually not sensitive to initialization. It allows finding optimal total tray numbers N1, N2 values and is directly used with the closed loop flow sheet. Within Pareto front, the effects of main variables FE/F and R1 on TAC and Eext are shown. There is a maximum Eext (resp. minimum R1) for a given R1 (resp. Eext). There exists an optimal efficiency indicator Eext,opt which corresponds to the optimal design with the lowest TAC. Eext,opt can be used as a complementary criterion for the evaluation of different designs. Through the analysis of extractive profile map, we explain why Eext increases following the decrease of FE and the increase of R1 and we relate them to the tray numbers. With the sake of further savings of TAC and increase of the environmental performance, double-effect heat integration (TEHI) and mechanical heat pump (MHP) techniques are studied. In TEHI, we propose a novel optimal partial HI process aiming at the most energy saving. In MHP, we propose the partial VRC and partial BF heat pump processes for which the coefficients of performance increase by 60% and 40%. Overall, optimal partial HI process is preferred from the economical view while full VRC is the choice from the environmental perspective.

Les arcs électriques de défaut se produisant entre deux câbles endommagés peuvent donner lieu à un phénomène appelé " arc tracking ", qui se caractérise par le maintien et la propagation de cet arc le long des câbles, entraînant leur ablation progressive. Dans un réseau aéronautique, un tel défaut peut avoir de graves conséquences lorsqu'il apparaît au sein d'un toron de câbles, d'autant plus qu'il est susceptible de se transférer à une structure avoisinante. Un dispositif expérimental a été développé pour l'étude de ce phénomène. Il est constitué d'une alimentation conçue selon des spécifications propres au domaine aéronautique, permettant de générer un signal continu ou alternatif pendant une durée réglable. Afin de se rapprocher des conditions de vol (pression réduite à haute altitude), les essais sont effectués au sein d'une enceinte fermée, soit à 1 bar, soit à 95 mbar. Trois types de câbles sont testés, un en aluminium et deux en cuivre. En régime continu, ils sont reliés au + et au - de l'alimentation, et à deux phases en régime alternatif. Une plaque en aluminium, représentant la structure de l'avion et connectée au neutre du générateur en régime alternatif, est placée en regard de la partie dénudée des câbles, là où se produit l'arc, permettant un éventuel transfert de l'arc depuis les câbles vers cette plaque. Chaque test s'accompagne de l'acquisition systématique des signaux de courant et de tension, et deux capteurs de flux radiatif sont positionnés autour de l'arc. Une caméra rapide permet la visualisation du comportement de l'arc au cours de l'essai. Enfin, les échantillons de câbles sont pesés avant et après chaque test. Un bilan de puissance est réalisé pour les différentes configurations testées (courant, pression, câbles), afin d'estimer la répartition de la puissance totale entre les électrodes (fusion et vaporisation des câbles, conduction, rayonnement) et la colonne de plasma (rayonnement, conduction, convection). La part transférée aux électrodes est estimée au moyen de la valeur de la chute de tension aux électrodes et du courant. Une partie de cette puissance aux électrodes est à l'origine de la fusion et de la vaporisation des câbles (le matériau isolant comme le métal). Celle-ci est estimée grâce à un calcul thermodynamique à partir de la masse de câble ablatée, en considérant que la totalité a été fondue et que 1% a été vaporisé. La puissance transmise à la colonne d'arc est en partie rayonnée, mais le spectre de longueurs d'onde inférieures à 200 nm est absorbé dès les premiers microns d'air, et une estimation est effectuée à partir du calcul coefficient d'émission nette. Une partie importante de l'étude a porté sur le transfert de l'arc à la plaque en aluminium, en fonction de la distance entre les câbles et cette plaque et selon un critère de température en face arrière, mesurée par thermographie infrarouge. Il a ainsi été montré qu'à pression réduite l'arc est beaucoup plus diffus, et a tendance à s'accrocher à la plaque en aluminium à des distances environ deux fois plus grandes qu'à pression atmosphérique. Cependant, la puissance totale disponible étant inférieure d'environ 20%, les dégâts à la plaque en aluminium sont moins importants. / Fault electric arcs occurring between two damaged wires may lead to a phenomenon called "arc tracking", which consists in a maintaining and propagating arc along the cables, causing their progressive ablation. In an aeronautical network, such a fault may have serious consequences if it happens within a wiring harness, especially as it is likely to transfer to a nearby structure. An experimental setup has been developed to study this phenomenon. It consists of a power supply designed in accordance with aeronautical specifications, which enables to generate a direct or alternating signal during an adjustable time. In order to reproduce flight conditions in a better way (low pressure at high altitude), tests are carried out within a closed chamber, whether at 1 bar pressure, or at 95 mbar pressure. Three types of cables are tested, one mainly made of aluminium and two mainly made of copper. In direct regime, they are connected to the + and the - poles of the generator, and to two phases in alternating regime. An aluminium plate, representing the aircraft structure and connected to the neutral in alternating regime, is placed in front of the stripped part of the cables, where the arc occurs, enabling a potential transfer of the arc from the cables toward the plate. Every test involves a systematic acquisition of the current and voltage signals, and two radiative flux sensors are positioned around the arc. A fast camera enables a viewing of the arc behaviour during the test. Finally, the sample is weighed before and after each test. A power balance is realised for the various tested configurations (current, pressure, cables), in order to estimate the distribution of the total power between the electrodes (fusion and vaporisation of the cables, but also conduction and radiation) and the plasma column (radiation, conduction, convection). The amount of power that is transferred to the electrodes is estimated with the value of the electrode voltage drop and the current. Part of this power makes the cables melt and vaporise (the insulating material as well as the metal), it is estimated with a thermodynamic calculation based on the ablated mass of cable, considering that the whole has been molten, and 1% vaporised. The amount of power transmitted to the arc column is partly radiated, but the wavelength spectrum emitted below 200 nm is absorbed through the very first microns in air, and estimation is made involving the calculation of the net emission coefficient. A significant part of the study was related to the transfer of the arc toward the aluminium plate, as a function of the distance between the cables and that plate, and according to a temperature criterion at the back side, by means of infrared thermography. Thus, it was shown that at low pressure, the arc is much less localised, and tends to transfer to the aluminium plate at distances around twice bigger than at atmospheric pressure. However, the total available power is around 20% smaller, and the damage caused to the aluminium plate is less severe.

Les matériaux (Si)GeSn sont très prometteurs pour les composants optiques sur puce fonctionnant dans le Moyen Infra-Rouge (MIR). Lors de cette thèse de doctorat, j’ai étudié le Dépôt Chimique en Phase Vapeur d’alliages GeSn. L’épitaxie basse température de Ge pur, de Ge dopé phosphore et d’alliages GeSi a tout d’abord été explorée. L’utilisation du digermane (Ge2H6) au lieu du germane (GeH4) nous a permis d’augmenter considérablement la vitesse de croissance du germanium à des températures en dessous de425 °C. Des concentrations très importantes en atome de P électriquement actifs ont été atteintes à 350 °C, 100 Torr en chimie Ge2H6 + PH3 (au maximum 7.5x1019 cm-3). Nous avons par la suite combiné le Ge2H6 avec le disilane (Si2H6) ou le dichlorosilane (SiH2Cl2) afin d’étudier la cinétique de croissance du GeSi à 475 °C, 100 Torr. Des concentrations de Ge définitivement plus élevées (77-82%) et une meilleure qualité de surface ont été obtenues avec le SiH2Cl2. Finalement, la croissance basse température d’alliages GeSn a été étudiée dans notre bâti d’épitaxie industriel 200 mm. Le digermane (Ge2H6) et le tétrachlorure d'étain (SnCl4) ont été utilisés pour explorer la cinétique de croissance et les mécanismes de relaxation des contraintes du GeSn. Une large gamme de concentrations en Sn, i.e. 6-16%, a été sondée et ces points de fonctionnement utilisés pour épitaxier des couches épaisses de GeSn partiellement relaxées. Nous avons ainsi mis en évidence l’intérêt d’utiliser une structure dite en escalier, en termes de qualité cristalline et de morphologie de surface. Un tel empilement, avec 16% de Sn dans sa partie supérieure, a montré une structure de bande directe et a conduit à une émission laser (dans des micro-disques) à une longueur d’onde de 3.1 µm. Ce laser a fonctionné jusqu’à 180 K et a un seuil de 377 kW/cm² à 25K. / (Si)GeSn is very promising for use in Mid Infra-Red (MIR) group-IV optical components on chip. During this PhD, I have studied the Reduced Pressure Chemical Vapor Deposition of GeSn alloys. The very low temperature epitaxy of pure Ge, heavily phosphorous doped Ge and Ge-rich SiGe alloys have first of all been investigated. Using digermane (Ge2H6) instead of germane (GeH4) enabled us to dramatically increase the Ge growth rate at temperatures 425 °C and lower. Very high electrically active P concentrations were obtained at 350 °C, 100 Torr with a Ge2H6 + PH3 chemistry (at most 7.5x1019 cm-3). We have then combined digermane with disilane (Si2H6) or dichlorosilane (SiH2Cl2) in order to study the GeSi growth kinetics at 475 °C, 100 Torr. Definitely higher Ge concentrations (77-82%) and smoother surfaces have been obtained with SiH2Cl2. We have then explored the low temperature epitaxy of high Sn content GeSn alloys in our 200 mm industrial RP-CVD tool. Digermane (Ge2H6) and tin tetrachloride (SnCl4) were used to investigate the GeSn growth kinetics and strain relaxation mechanisms. Large range of Sn concentrations, i.e. in the 6-16% range, was probed and data points used to grow thick, partially relaxed GeSn layers. The benefits of using Step-Graded structures, in terms of crystalline quality and surface morphology, was conclusively demonstrated for thick GeSn layers with high Sn contents. Such a stack, with 16% of Sn in the top part, was direct bandgap and led to a laser operation (in micro-disks) up to 180 K at an emission wavelength of 3.1 µm and with a lasing threshold of 377 kW/cm² at 25K.

Ce projet de thèse porte sur le traitement de films de graphène dans la post-décharge en flux de plasmas micro-ondes d’azote à pression réduite. Différentes considérations de contamination de surface des échantillons se sont avérées cruciales pour ce travail. Par exemple, en présence d’hydrocarbures, les traitements dans les différentes régions de la post-décharge montrent des profils de production de dommages, d’incorporation d’azote et de fonctionnalisation de contaminants distincts. Le traitement agressif qu’offre la post-décharge proche résulte en la formation de complexes amorphes graphène-hydrocarbures responsables d’une forte hausse de la teneur en azote (jusqu’à 49%) pour des désordres modérés (D:G = 1.3). Pour les traitements dans la post-décharge lointaine, les hydrocarbures jouent un rôle de couche protectrice permettant une incorporation monotone (jusqu’à 18%) à très faible dommage (D:G < 0.3). Les espèces azotées sont néanmoins faiblement liées de sorte que le transfert vers un substrat de SiO2 engendre une perte importante (> 80%) de la teneur en azote. Des considérations d’inhomogénéité de surface des films de graphène ont motivé le développement d’une nouvelle méthode d’analyse des cartographies Raman obtenues par un imageur hyperspectral. L’étude des spectres Raman au niveau des domaines versus aux joints de grains ont permis de mettre en évidence un mécanisme d’auto-réparation des joints de grains relié à l’anisotropie de la migration des adatomes de carbone en surface. L’accumulation de ceux-ci aux joints de grains mène à une émission d’adatomes responsable de l’annihilation de paires de Frenkel. Dans les plasmas azotés, il s’avère que ce mécanisme est également responsable d’une incorporation sélective d’azote aux domaines de croissance du graphène. Lorsque amorphisé, le dopage sélectif s’estompe puisque le transport des adatomes de carbone aux joints de grains, ainsi que l’accumulation essentielle au processus d’auto-réparation, deviennent entravés. Finalement, la recombinaison en surface d’atomes d’azote et la désexcitation de métastables N2(A) sont identifiés comme principaux agents pour la production de dommages dans la post-décharge en flux d’azote. Un modèle d’incorporation impliquant la formation de dommages et l’adsorption d’atomes d’azote est proposé. En présence d’espèces oxydantes dans la post-décharge d’azote, la formation de dommages demeure limitée par les populations de N et de N2(A). / This thesis project deals with the treatment of graphene films in the flowing afterglow of microwave nitrogen plasmas at reduced pressure. Various surface contamination considerations were found to be crucial for this work. For example, in the presence of hydrocarbons, the treatments in the different regions of the afterglow show distinct damage production, nitrogen incorporation and contaminant functionalization profiles. The aggressive treatment offered by the early afterglow results in the formation of amorphous graphene-hydrocarbon complexes responsible for a sharp increase in the nitrogen content (up to 49%) at moderate disorders (D: G = 1.3). For the treatments in the late afterglow, the hydrocarbons act as a protective layer, allowing a monotonic incorporation (up to 18%) with very low damage (D: G < 0.3). Nitrogenous species are found to be weakly bound so that transfer to an SiO2 substrate generates a significant loss (>80%) of the nitrogen content. Considerations of surface inhomogeneity of graphene films have motivated the development of a new analysis method of Raman maps obtained by hyperspectral imager. The study of Raman spectra at growth domain versus grain boundary has revealed a self-healing mechanism of grain boundaries linked to the anisotropy of the migration of carbon adatoms at the surface. The accumulation of these at grain boundaries leads to an emission of atoms responsible for the annihilation of Frenkel pairs. In nitrogenous plasmas, this mechanism is also found to be responsible for the selective incorporation of nitrogen into the growth domains of the graphene. For amorphous graphene, selective doping fades as the transport of carbon adatoms to grain boundaries, and therefore the accumulation essential to the self-healing process, becomes impeded. Finally, the surface recombination of nitrogen atoms and the de-excitation of metastable N2(A) are identified as the main agents defect generation in the nitrogen flowing afterglow. An incorporation model involving the formation of damage and adsorption of nitrogen atoms is proposed. In the presence of oxidizing species in the nitrogen afterglow, damage formation remains limited by populations of N and N2(A).

Silicon technologyhas been seekingfor a monolithic solution for a chip where data processing and data communication is performed in the CMOS part and the photonic component, respectively. Traditionally, silicon has been widely considered for electronic applications but not for photonic applications due to its indirect bandgap nature. However, band structure engineering and manipulation through alloying Si with Ge and Sn has opened new possibilities. Theoretical calculations show that it is possible to achieve direct transitions from Ge ifit is alloyed with Sn. Therefore, a GeSn system is a choice to get a direct bandgap. Extending to ternary GeSnSi and quaternary GeSnSiCstructures grown on Si wafers not only makes the bandgap engineering possible but also allowsgrowing lattice matched systems with different strain and bandgaps located in the infrared region. Different heterostructures can be designed and fabricated for detecting lightas photonic sensing oremitting the light as lasers. Alloying not only makes engineering possible but it also induces strain which plays an important role for electronic applications. Theoretical and experimental works show that tensile strain could increase the mobility, which is promising for electronic devices where high mobility channels for high performance MOSFETs is needed to speed up the switching rate. On the other hand, high n-doping in tensile strains in p-i-n structures makesΓ band transitions most probable which is promising for detection and emission of the light. As another benefit of tensile strain, the direct bandgap part shrinks faster than the indirect one if the strain amount is increased. To get both electronic and photonic applications of GeSn-based structures, two heterostructures (Ge/GeSn(Si)/GeSi/Ge/Si and Ge/GeSn/Si systems), including relaxed and compressive strained layers used to produce tensile strained layers, were designed in this thesis. The low temperature growth is of key importance in this work because the synthesis of GeSn-based hetrostructures on Si wafers requires low thermal conditions due tothe large lattice mismatch which makes them metastable. RPCVD was used to synthesize theseheterostructures because not only it offers a low temperature growth but also because it is compatible with CMOS technology. For utilization of these structures in devices, n-type and p-type doping of relaxed and compressive strained layers were developed. HRRLMs, HRTEM, RBS, SIMS, and FPP techniques were employed to evaluatestrain, quality, Sn content and composition profile of the heterostructures. The application of GeSn-based heterostructures is not restricted to electronics and photonics. Another application investigated in this work is photovoltaics. In competition with Si-based solar cells, which have, or areexpected to have,high stability and efficiency, thirdgeneration solar cells offer the use of low cost materials and production and can therefore be an alternative for future light energy conversion technology. Particularly, quantum dot sensitized solar cells are associated with favorable properties such as high extrinsic coefficients, size dependent bandgaps and multiple exciton generation and with a theoretical efficiencyof 44%. In this work, two categories of QDs, Cd-free and Cd-based QDs were employed as sensitizers in quantum dot sensitized solar cells (QDSSCs). Cd-based QDs have attracted large interest due to high quantum yield,however, toxicityremains still totheir disadvantage. Mn doping as a bandgap engineering tool for Cd-based type IIZnSe/CdS QDs wasemployed to boostthe solar cell efficiency. Theoretical and experimental investigations show that compared to single coreQDSSCs,typeII core-shells offer higher electron-hole separation due to efficient band alignment where the photogenerated electrons and holes are located in the conduction band of the shell and valence band of the core, respectively. This electron-hole separation suppresses recombination and by carefully designing the band alignment in the deviceit can increase the electron injection and consequently the power conversion efficiency of the device. Considering eco-friendly and commercialization aspects, three different “green” colloidal nanostructures having special band alignments, which are compatible for sensitized solar cells, were designed and fabricated by the hot injection method. Cu2GeS3-InP QDs not only can harvest light energy up to the infraredregion but can also be usedastypeII QDs. ZnS-coating was employed as a strategy to passivate the surface of InP QDs from interaction with air and electrolyte. In addition, ZnS-coating and hybrid passivation was applied for CuInS2QDs to eliminate surface traps. / <p>QC 20151125</p>

Epitaxially grown SiGe(C) materials have a great importance for many device applications. In these applications, (strained or relaxed) SiGe(C) layers are grown either selectively on the active areas, or on the entire wafer. Epitaxy is a sensitive step in the device processing and choosing an appropriate thermal budget is crucial to avoid the dopant out–diffusion and strain relaxation. Strain is important for bandgap engineering in (SiGe/Si) heterostructures, and to increase the mobility of the carriers. An example for the latter application is implementing SiGe as the biaxially strained channel layer or in recessed source/drain (S/D) of pMOSFETs. For this case, SiGe is grown selectively in recessed S/D regions where the Si channel region experiences uniaxial strain.The main focus of this Ph.D. thesis is on developing the first empirical model for selective epitaxial growth of SiGe using SiH2Cl2, GeH4 and HCl precursors in a reduced pressure chemical vapor deposition (RPCVD) reactor. The model describes the growth kinetics and considers the contribution of each gas precursor in the gas–phase and surface reactions. In this way, the growth rate and Ge content of the SiGe layers grown on the patterned substrates can be calculated. The gas flow and temperature distribution were simulated in the CVD reactor and the results were exerted as input parameters for the diffusion of gas molecules through gas boundaries. Fick‟s law and the Langmuir isotherm theory (in non–equilibrium case) have been applied to estimate the real flow of impinging molecules. For a patterned substrate, the interactions between the chips were calculated using an established interaction theory. Overall, a good agreement between this model and the experimental data has been presented. This work provides, for the first time, a guideline for chip manufacturers who are implementing SiGe layers in the devices.The other focus of this thesis is to implement SiGe layers or dots as a thermistor material to detect infrared radiation. The result provides a fundamental understanding of noise sources and thermal response of SiGe/Si multilayer structures. Temperature coefficient of resistance (TCR) and noise voltage have been measured for different detector prototypes in terms of pixel size and multilayer designs. The performance of such structures was studied and optimized as a function of quantum well and Si barrier thickness (or dot size), number of periods in the SiGe/Si stack, Ge content and contact resistance. Both electrical and thermal responses of such detectors were sensitive to the quality of the epitaxial layers which was evaluated by the interfacial roughness and strain amount. The strain in SiGe material was carefully controlled in the meta–stable region by implementingivcarbon in multi quantum wells (MQWs) of SiGe(C)/Si(C). A state of the art thermistor material with TCR of 4.5 %/K for 100×100 μm2 pixel area and low noise constant (K1/f) value of 4.4×10-15 is presented. The outstanding performance of these devices is due to Ni silicide contacts, smooth interfaces, and high quality of multi quantum wells (MQWs) containing high Ge content.The novel idea of generating local strain using Ge multi quantum dots structures has also been studied. Ge dots were deposited at different growth temperatures in order to tune the intermixing of Si into Ge. The structures demonstrated a noise constant of 2×10-9 and TCR of 3.44%/K for pixel area of 70×70 μm2. These structures displayed an improvement in the TCR value compared to quantum well structures; however, strain relaxation and unevenness of the multi layer structures caused low signal–to–noise ratio. In this thesis, the physical importance of different design parameters of IR detectors has been quantified by using a statistical analysis. The factorial method has been applied to evaluate design parameters for IR detection improvements. Among design parameters, increasing the Ge content of SiGe quantum wells has the most significant effect on the measured TCR value. / QC 20110405