Adsorption of monolayers and multilayers of metal-free and metal phthalocyanines molecules on metal surfaces has been investigated using complementary microscopic and synchrotron-based spectroscopic techniques. It was observed by STM measurements that at monolayer coverage the adsorption direction of the metal-free phthalocyanine molecules with respect to the gold surface vary as a function of temperature, i.e. at room temperature (RT) and low temperature (LT). It was explained by the difference in strength of intermolecular and adsorbate-substrate interactions at room and low temperatures. Nature of the interaction between adsorbed species and the surfaces as a function of coverage has been further characterized by XPS measurements. Binding energy shifts as a function of coverage have been attributed to initial- and final-state effects, the latter being due to different core-hole screening for the different molecular coverage. The alignment of molecular films at both monolayer and multilayer coverages, which has been determined by XAS measurements in several cases, is also dependent upon the relative strength of molecule-molecule versus molecule-substrate interaction. Parallel alignment of the molecular film with respect to the surface is the result of significant interaction between the adsorbate and the substrate, whilst standing geometry of the molecular film is due to more significant intermolecular interactions. DFT simulations have provided further information on the nature of the adsorbate-substrate interaction as well as contribution of different molecular orbitals in XPS and XAS spectra. Moreover, investigation of alkali interaction with the phthalocyanine films revealed a significant modification in their geometric and electronic structures due to charge transfer from the alkali metal to the molecular film. However, no sign of metallization of the molecules has been observed by spectroscopic and microscopic studies.

Die Entwicklung der Mikroelektronik wird durch eine fortschreitende Miniaturisierung der Bauelemente geprägt. Infolge einer Reduzierung der Querschnittflächen von Leitbahnstrukturen erhöht sich die elektrische Leistungsdichte und das Metallisierungssystem bestimmt zunehmend die Übertragungsgeschwindigkeiten. Kupfer repräsentiert hierbei das verbreitetste Leitbahnmaterial und wird vorwiegend mittels elektrochemischer Abscheidung in vergrabene Damaszen-Strukturen eingebracht. Die vorliegende Dissertation beschreibt Möglichkeiten für eine Optimierung von Kupferleitbahnen für höchstintegrierte Schaltkreise. Von besonderem Interesse sind hierbei die Gefügequalität und der Reinheitsgrad. Es erfolgen umfangreiche werkstoffanalytische und elektrochemische Untersuchungen zur Charakterisierung von Depositionsmechanismen, des Einbaus von Fremdstoffen, des Mikrogefüges nach der Abscheidung und der Mikrogefügeumwandlung. In einem abschließenden Forschungsschwerpunkt werden Kupfer-Damaszen-Teststrukturen mit unterschiedlichen Gehalten nichtmetallischer Verunreinigungen hergestellt und entsprechenden Lebensdauerexperimenten unterzogen. Hierdurch gelingt eine Evaluierung des Einflusses jener Verunreinigungen auf die Elektromigrationsbeständigkeit von Kupferleitbahnen. Die Arbeit umfasst daher das gesamte Spektrum von der Grundlagenforschung bis zur Applikation von elektrochemisch abgeschiedenen Kupferdünnschichtmetallisierungen.

[pt] O pó de aciaria (fração Fina-F e fração Grossa-G) gerado no sistema de despoeiramento à seco dos gases de exaustão do conversor LD, e o pó de alto forno-AF recuperado pelo sistema de tratamento de gases do setor de redução (coletor de gases), têm papel relevante entre os materiais secundários gerados nos vários elos da cadeia produtiva de uma siderúrgica integrada, seja pelas quantidades produzidas, seja por suas composições. Por serem portadores principalmente de unidades de ferro e carbono e algumas vezes zinco, esses resíduos são sempre alvo de iniciativas tecnológicas que objetivem recuperá-los ou reciclá-los. Além disso, os materiais particulados gerados pelo sistema de despoeiramento a seco, diferentemente dos à úmido, ainda carecem de estudos aprofundados para suas reciclagens. Embora antiga, a briquetagem atualmente vem se tornando uma tecnologia cada vez mais importante entre os processos de aglomeração. Assim, nesta Tese foi estudado, numa primeira etapa, a viabilidade de fabricação dos chamados briquetes F-G simples, constituídos apenas pelos pós Finos e Grossos, nas proporções percentuais de 50-50 e 70-30, respectivamente, e o exame teórico e experimental de seus usos como carga ferrosa nos processos de redução e como materiais alternativos às sucatas e pelotas, quando adicionados ao aço líquido do conversor LD para o controle de sua temperatura. Na fabricação dos briquetes F-G simples, também buscou-se testar os aglomerantes cimento ARI e melaço de cana de açúcar, isoladamente ou quando misturados, atendendo às relações água/cimento de 0,5 e água/melaço de 0,7. O processo experimental de cura a frio dos aglomerados se estendeu até 28 dias. A resistência à compressão obtida em prensa hidráulica instrumentada foi o principal parâmetro para avaliar a qualidade mecânica dos briquetes. A metodologia experimental envolveu a técnica do planejamento fatorial, 2(k), níveis (mínimo e máximo), com três variáveis (resíduos, aglomerantes e água). Nos resultados verificou-se que a resistência à compressão dos briquetes F-G simples, usando o binômio cimento-melaço sempre apresentou valores mais elevados do que os briquetes quando aglutinados com as duas substancias isoladamente. Além disso, dentre os aglomerados produzidos os de teores mais elevados de fração Grossa (briquetes 50-50), apresentaram maior resistência mecânica que os briquetes tipo 70-30. Em relação aos efeitos de resfriamento que provocam quando adicionados ao aço liquido, os balanços térmicos mostraram que os briquetes do tipo 70-30 apresentariam melhores índices no controle da temperatura do banho de aço, que os do tipo 50-50. A fim de verificar como se comportariam os briquetes F-G anteriores, quando se adicionava o pó de coletor de AF nas suas constituições como fonte supridora de carbono e apenas o cimento ARI como aglutinante, foram produzidos os denominados briquetes autorredutores, também dos tipos F-G, 50-50 e 70-30. Além da viabilidade de fabricação desses aglomerados, foram determinadas suas qualidades mecânicas e levantadas suas metalizações em ensaios de redução nas temperaturas de 1100 graus Celsius e 1150 graus Celsius. O estudo cinético da autorredução foi realizado avaliando-se o grau de conversão a ferro metálico e examinada a fenomenologia de sua evolução. Os resultados evidenciaram que o grau de conversão metálica cresceu com o aumento da temperatura e com a quantidade da fonte de carbono, que a metalização apresentou uma morfologia final do tipo shell layer e que o modelo cinético testado, tipo reação continua, apresentou uma correlação acima de 99 por cento. Além disso, os balanços de energia mostraram que o efeito de resfriamento imposto ao aço liquido pelos briquetes F-G autorredutores, sempre se mostrou superior aos dos briquetes F-G simples. Adicionalmente, afim de melhor interpretar os resultados obtidos foram realizados testes adicionais, como o de reatividade do coque metalúrgico, via a norma ASTM D5341-99 e por aná / [en] The steel dusts (fine-F and coarse-G fractions) generated in the dry dedusting equipment of the LD converter exhaust system, and in the blast furnace-AF dust collector, play a relevant role among secondary materials generated in the various steps of the integrated steelmaking chain, either by the quantities produced and their compositions. Because they mainly contain iron and carbon units and sometimes zinc in their compositions, actually these wastes are being the target of several technological initiatives, aiming to recover or recycle them. Moreover, the particulate materials generated by the LD dry dedusting system, unlike those collected in the wet system of the same LD processes, still lack in-depth studies for recycling. Nowadays briquetting is increasing in importance among agglomeration processes, mainly due to its feature in treat particulate materials with a wide range of size. This thesis studied, in a first stage, the feasibility of manufacturing the so-called simple F-G briquettes, in the proportions of 50-50 and 70-30, respectively, as well as their theoretically and experimentally possibilities to be charged as a ferrous burden in reduction processes and as an alternative material to the scrap and pellets, when used to control the liquid steel temperature in LD converters. In the manufacture of the simple F-G briquettes, was also tested the binders ARI cement and sugarcane molasses, alone or when mixed, taking into account the water / cement ratio of 0,5 and the water / molasses ratio of 0,7. For the briquettes studied in this research, all cure operations lasted for up to 28 days and the compressive strength parameter obtained to evaluate the mechanical quality of the briquettes. The experimental methodology involved the technique of factorial planning, 2(k) levels (minimum and maximum), with three variables (residues, agglomerates and water). The results showed that the compressive strengths of the simple F-G briquettes, when using the cement-molasses mixture, always achieved higher values than that for briquettes using the cement or molasses separately. Moreover, the higher content of coarser fraction (briquettes 50-50) always leads to higher mechanical resistance than the finer one (70-30). On the other hand, the energy balances showed that the simple F-G briquettes 70-30, have presented the better cooling indexes for the liquid steel temperature control than the 50-50 briquettes. Regarding the second part of the thesis, two types of F-G self-reducing briquettes were also produced, containing stoichiometric and 10 percent excess of BF-collector dusts. After curing, they were tested on compression and reduced in temperatures of 1100 Celsius degrees and 1150 Celsius degrees. The kinetic study of the self-reducing briquettes was carried out evaluating the metallic iron conversion and the metallic iron phenomenology and morphology formation. The results showed: a) that the iron conversion increased as higher the temperature and amount of carbon; b) that the iron metallization presented a shell-layer type morphology and, c) that the continuous-reaction type kinetic model, adjusted very well the experimental reduction results, with a correlation factor above 99 percent. Additionally, in order to better understand the experiment results, the metallurgical coke reactivity was obtained using the ASTM D5341-99 test and the Differential Thermogravimetric analyzes (DTG), as well as confirmed the hydrated water amount in the passivated F and G dusts, also using the DTG methodology. Finally, considering the manufacturing feasibility of the both, simple and self-reducing F-G briquettes, the following could be also marked: I) The use of both briquettes type for liquid steel temperature control in LD converters, as effective alternative materials to scraps and pellets, considering the following comparative cooling indexes: a) 2,1 and 2,4 times the scrap, for the self-reducing briquettes 50-50 and 70-30, respectively, both with 10 percent excess; b) 1,7 and 1,9 times the scrap, for the simple briquettes, 50-50 and 70

abstract: Programmable metallization cell (PMC) technology employs the mechanisms of metal ion transport in solid electrolytes (SE) and electrochemical redox reactions in order to form metallic electrodeposits. When a positive bias is applied to an anode opposite to a cathode, atoms at the anode are oxidized to ions and dissolve into the SE. Under the influence of the electric field, the ions move to the cathode and become reduced to form the electrodeposits. These electrodeposits are filamentary in nature and persistent, and since they are metallic can alter the physical characteristics of the material on which they are formed. PMCs can be used as next generation memories, radio frequency (RF) switches and physical unclonable functions (PUFs). The morphology of the filaments is impacted by the biasing conditions. Under a relatively high applied electric field, they form as dendritic elements with a low fractal dimension (FD), whereas a low electric field leads to high FD features. Ion depletion effects in the SE due to low ion diffusivity/mobility also influences the morphology by limiting the ion supply into the growing electrodeposit. Ion transport in SE is due to hopping transitions driven by drift and diffusion force. A physical model of ion hopping with Brownian motion has been proposed, in which the ion transitions are random when time window is larger than characteristic time. The random growth process of filaments in PMC adds entropy to the electrodeposition, which leads to random features in the dendritic patterns. Such patterns has extremely high information capacity due to the fractal nature of the electrodeposits. In this project, lateral-growth PMCs were fabricated, whose LRS resistance is less than 10Ω, which can be used as RF switches. Also, an array of radial-growth PMCs was fabricated, on which multiple dendrites, all with different shapes, could be grown simultaneously. Those patterns can be used as secure keys in PUFs and authentication can be performed by optical scanning. A kinetic Monte Carlo (KMC) model is developed to simulate the ion transportation in SE under electric field. The simulation results matched experimental data well that validated the ion hopping model. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2015

abstract: Counterfeiting of goods is a widespread epidemic that is affecting the world economy. The conventional labeling techniques are proving inadequate to thwart determined counterfeiters equipped with sophisticated technologies. There is a growing need of a secure labeling that is easy to manufacture and analyze but extremely difficult to copy. Programmable metallization cell technology operates on a principle of controllable reduction of a metal ions to an electrodeposit in a solid electrolyte by application of bias. The nature of metallic electrodeposit is unique for each instance of growth, moreover it has a treelike, bifurcating fractal structure with high information capacity. These qualities of the electrodeposit can be exploited to use it as a physical unclonable function. The secure labels made from the electrodeposits grown in radial structure can provide enhanced authentication and protection from counterfeiting and tampering. So far only microscale radial structures and electrodeposits have been fabricated which limits their use to labeling only high value items due to high cost associated with their fabrication and analysis. Therefore, there is a need for a simple recipe for fabrication of macroscale structure that does not need sophisticated lithography tools and cleanroom environment. Moreover, the growth kinetics and material characteristics of such macroscale electrodeposits need to be investigated. In this thesis, a recipe for fabrication of centimeter scale radial structure for growing Ag electrodeposits using simple fabrication techniques was proposed. Fractal analysis of an electrodeposit suggested information capacity of 1.27 x 1019. The kinetics of growth were investigated by electrical characterization of the full cell and only solid electrolyte at different temperatures. It was found that mass transport of ions is the rate limiting process in the growth. Materials and optical characterization techniques revealed that the subtle relief like structure and consequently distinct optical response of the electrodeposit provides an added layer of security. Thus, the enormous information capacity, ease of fabrication and simplicity of analysis make macroscale fractal electrodeposits grown in radial programmable metallization cells excellent candidates for application as physical unclonable functions. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2017

À l'échelle industrielle, la métallisation de la face avant des cellules photovoltaïques est réalisée grâce au procédé de sérigraphie depuis plus de 40 ans. Une pâte à base d'argent est imprimée avant d'être recuite à haute température. La robustesse, la simplicité et la haute cadence de production de ce procédé ont largement contribué à son succès. L'étape de métallisation est critique dans la chaîne de fabrication des cellules. D'un côté, les propriétés des contacts déposés déterminent les performances finales des cellules. D'un autre côté, plus de 7% de la consommation mondiale d'argent sont déjà destinés à l'industrie photovoltaïque. Avec les prévisions de croissance exponentielle de ce secteur, la quantité d'argent déposée lors de cette étape devient de plus en plus cruciale car elle régit le coût final des cellules. Elle dépend également de la qualité des contacts imprimés. Il est donc important d'optimiser le procédé de sérigraphie pour limiter la masse d'argent imprimée et maximiser le rendement des cellules. Les travaux présentés dans la première partie de cette thèse sont focalisés sur ces deux aspects. Dans un premier temps, le comportement rhéologique des pâtes de sérigraphie est étudié. Par la suite, une étude multifactorielle combinée à des simulations des pertes de puissance permet d'évaluer l'influence des paramètres de la sérigraphie sur le rendement des cellules et la masse d'argent déposée. Ces travaux ont conduit à la fabrication de cellules caractérisées par un rendement moyen de 19,0% à l'échelle industrielle. Le procédé de sérigraphie reste couteux et de nombreuses solutions alternatives sont à l'étude. En effet, la microstructure hétérogène des contacts cause des pertes électriques non négligeables en comparaison des cellules à haut rendement. Par ailleurs, la résolution limitée de ce procédé ne permet plus de réduire les dimensions des impressions, ce qui a un impact direct sur les pertes optiques et la masse d'argent déposée. Enfin, l'optimisation simultanée des propriétés électriques et géométriques des contacts complexifie son contrôle à l'échelle industrielle. Le concept double couche est une alternative innovante qui permet de s'affranchir de ces limitations. Une première couche est d'abord imprimée pour limiter la largeur initiale des contacts et améliorer l'interface avec la cellule. Une seconde couche de métal pur, déposée par voie électrolytique, vient épaissir cette dernière pour optimiser la hauteur et la conductivité de la grille de métallique. Dans le même temps, cette étape permet de contrôler précisément la masse d'argent déposée. Plusieurs solutions sont disponibles pour réaliser l'impression de la première couche. Grâce à sa flexibilité et à sa très haute cadence de production, le procédé de flexographie semble répondre au cahier des charges d'un tel dépôt dans des conditions industrielles. La seconde partie des travaux exposés dans cette thèse traite du développement de cette technique d'impression. Tout d'abord, le comportement rhéologique de plusieurs encres dérivées d'une pâte de sérigraphie classique est étudié. Dans un second temps, le procédé de flexographie est adapté au dépôt de lignes pouvant être épaissies par voie électrolytique (procédé LIP). Le potentiel de ce procédé est ensuite évalué à l'aide de modélisations du rendement et de la masse d'argent déposée. Finalement, la faisabilité du concept est démontrée grâce à la fabrication d'une cellule caractérisée par un rendement prometteur de 17,9%. / At an industrial scale, the front side metallization of solar cells is performed by screen printing for 40 years. A silver-based paste is printed before a high temperature annealing. This simple and robust process enables a high throughput. However, the metallization is a critical step in production lines. On the one hand, the contact properties affect the final cell performances. On the other hand, the photovoltaic industry already accounts for 7% of the world's silver consumption. With the expected exponential growth of this sector, the mass of silver per cell becomes crucial as it governs their final cost. Consequently, it is mandatory to optimize the screen printing process to limit the amount of deposited silver and maximize the solar cell efficiency. The first part of this study focused on these two aspects. First, the rheological behavior of screen printing pastes is investigated. Then, a multifactorial study is combined with power loss simulations to assess the effect of screen printing parameters on the cell efficiency and the deposited silver mass. Besides, these studies have lead to an average cell efficiency of 19,0% at an industrial scale. To ensure the photovoltaic industry growth, the screen printing process should be replaced in coming years. Indeed, the heterogeneous contact microstructure causes significant electrical losses in comparison to high-efficiency cells. Moreover, the limited resolution of this process does no longer allow a contact width reduction, which has a direct impact on the optical losses and the silver mass per cell. Finally, the simultaneous optimization of the electrical and geometrical contact properties is difficult at an industrial scale. The seed and plate concept is an innovative solution that overcomes these limitations. First, a seed layer is printed to reduce the initial contact width and improve its interface with the cell. Then, a second layer is electrolytically grown to improve the conductivity and the height of the metal grid. Besides, this step enables an accurate control of the deposited silver amount. Several solutions are available to print the first layer. Because of a high throughput and flexibility, the flexographic printing process seems particularly well suited to meet the seed layer requirements at an industrial level. The second part of this study focuses on the development of this process. First, the rheological behavior of several inks is studied. Secondly, the flexographic printing process is adapted to print fine lines that can be thickened by light induced plating (LIP). The potential of this metallization scheme is then assessed using a simulation of cell performances and silver consumption. Finally, a promising 17,9% cell efficiency demonstrates the concept feasibility.

La projection thermique cold spray consiste en l'envol de poudres à haute vitesse sur une cible : le substrat. Leur adhérence et leur accumulation mène à des revêtements plus ou moins denses, utilisés dans le domaine automobile, biomédical, etc. La première étape de construction du dépôt passe par un contact entre la poudre et le substrat. Il est admis que la liaison créée est mécanique et, si la nature des matériaux le permet, métallurgique. Cette étude permet de statuer sur ces deux composantes. Pour cela, deux systèmes privilégiant l'une ou l'autre, sont choisis. L'ancrage mécanique est vu au travers de la métallisation de polymère avec l'emploi d'aluminium projeté sur polyamide 6,6. La liaison métallurgique est abordée avec l'emploi de titane sur un substrat plus rigide en TA6V. Avant d'étudier les mécanismes de liaison, une étape d'élaboration des dépôts est réalisée balayant de nombreux paramètres « procédé » et différentes propriétés des matériaux (température, granulométrie). Des outils sont déployés pour connaître les conditions d'impact : la vitesse de particule par DPV2000, la température du substrat par thermographie infra-rouge et la température des particules par voie numérique. L'ancrage mécanique dans le polymère est décrit grâce à l'étude de l'impact de particules élémentaires ainsi que de la rugosité d'interface 2D (coupes micrographiques) et 3D (laminographie X). Le gradient de porosité est également quantifié. La liaison métallurgique est étudiée par MET. Au préalable, la simulation numérique par éléments finis est employée pour retracer la phénoménologie de l'impact ainsi que quantifier les déformations et les températures locales atteintes à l'interface. La morphologie simulée des particules à l'impact est comparée à celles observées dans des conditions réelles de projection. Enfin, l'adhérence des différents dépôts est évaluée par essai « plot collé » et les faciès de rupture observés. L'influence de la morphologie de surface est étudiée avec des prétraitements de sablage et de structuration laser. / Cold Spray consists in the high-speed spray of powder particles onto a target; namely the substrate. Their adhesion and accumulation leads to a more or less dense coating to be used in the automotive, the biomedical… areas. The first stage of coating results from a powder to substrate contact. Bonding is due to mechanical anchoring and, depending on the involved materials, to metallurgical interaction. This study helps to rule on these two components. For this, two systems, which promote either mechanical or metallurgical mechanism separately, are selected. Mechanical anchoring is studied through polymer metallization using of aluminum for spraying onto polyamide 6,6. Metallurgical bonding is studied using titanium onto Ti-6Al-4V. Before studying the bonding mechanisms, the spraying process is investigated using many process parameters and materials properties (temperature, particle size…). Advanced tools are employed to determine impact conditions; i.e. particle velocity by DPV2000, substrate temperature by infrared thermography and particle temperature by numerical calculation. Mechanical anchoring onto the polymer is described through the analysis of elementary particle impacts and through 2D (micrograph sections) and 3D (laminography) study of interface roughness. The porosity gradient is also quantified. Metallurgical bonding is studied by TEM. Before that, a finite element simulation is used to go into the phenomenology of the impact and to quantify the local deformation and temperature at the interface. The simulated particle morphology is compared to those observed in real spraying conditions. Lastly, deposit adhesion is assessed by pull-off testing and the fractured surface is observed. The influence of the substrate surface morphology is exhibited using sand-blasting and laser structuring pretreatments.

Aluminum was deposited onto both Teflon AF and Parylene AF surfaces by chemical vapor deposition of trimethylaluminum. This work shows that similar thin film (100 Angstroms) aluminum oxide adlayers form on both polymers at the low temperature dosing conditions used in the studies. Upon anneal to room temperature and above, defluorination of the polymer surfaces increased and resulted in fluorinated aluminum oxide adlayers; the adlayers were thermally stable to the highest temperatures tested (600 K). Angle-resolved spectra showed higher levels of fluorination toward the polymer/adlayer interface region. Copper films were also deposited at low temperature onto Teflon AF using a copper hexafluoroacetylacetonate-cyclooctadiene precursor. Annealing up to 600 K resulted in the loss of precursor ligands and a shift to metallic copper. As with aluminum adlayers, some polymer defluorination and resulting metal (copper) fluoride was detected. Parylene AF and polystyrene films surfaces were modified by directly dosing with water vapor passed across a hot tungsten filament. Oxygen incorporation into polystyrene occurred exclusively at aromatic carbon sites, whereas oxygen incorporation into parylene occurred in both aromatic and aliphatic sites. Oxygen x-ray photoelectron spectra of the modified polymers were comparable, indicating that similar reactions occurred. The surface oxygenation of parylene allowed enhanced reactivity toward aluminum chemical vapor deposition. Silicon-carbon (Si-Cx) films were formed by electron beam bombardment of trimethylvinylsilane films which were adsorbed onto metal substrates at low temperatures in ultra-high vacuum. Oxygen was also added to the films by coadsorbing water before electron beam bombardment; the films were stable to more than 700 K, with increasing silicon-oxygen bond formation at elevated temperatures. Copper metal was sputter deposited in small increments onto non-oxygenated films. X-ray photoelectric spectra show three-dimensional copper growth (rather than layer-by-layer growth), indicating only weak interaction between the copper and underlying films. Annealing at elevated temperatures caused coalescence or growth of the copper islands, with spectra indicating metallic copper rather than copper oxide.

abstract: Programmable Metallization Cell (PMC) devices are, in essence, redox-based solid-state resistive switching devices that rely on ion transport through a solid electrolyte (SE) layer from anode to cathode. Analysis and modeling of the effect of different fabrication and processing parameter/conditions on PMC devices are crucial for future electronics. Furthermore, this work is even more significant for devices utilizing back-end- of-line (BEOL) compatible materials such as Cu, W, their oxides and SiOx as these devices offer cost effectiveness thanks to their inherent foundry-ready nature. In this dissertation, effect of annealing conditions and cathode material on the performance of Cu-SiOx vertical devices is investigated which shows that W-based devices have much lower forming voltage and initial resistance values. Also, higher annealing temperatures first lead to an increase in forming voltage from 400 °C to 500 °C, then a drastic decrease at 550 °C due to Cu island formation at the Cu/SiOx interface. Next, the characterization and modeling of the bilayer Cu2O/Cu-WO3 obtained by annealing the deposited Cu/WO3 stacks in air at BEOL-compatible temperatures is presented that display unique characteristics for lateral PMC devices. First, thin film oxidation kinetics of Cu is studied which show a parabolic relationship with annealing time and an activation energy of 0.70 eV. Grown Cu2O shows a cauliflower-like morphology where feature size on the surface increase with annealing time and temperature. Then, diffusion kinetics of Cu in WO3 is examined where the activation energy of diffusion of Cu into WO3 is calculated to be 0.74 eV. Cu was found to form clusters in the WO3 host which was revealed by imaging. Moreover, using the oxidation and diffusion analyses, a Matlab model is established for modeling the bilayer for process and annealing-condition optimization. The model is built to produce the resulting Cu2O thickness and Cu concentration in Cu-WO3. Additionally, material characterization, preliminary electrical results along with modeling of lateral PMC devices utilizing the bilayer is also demonstrated. By tuning the process parameters such as deposited Cu thickness and annealing conditions, a low-resistive Cu2O layer was achieved which dramatically enhanced the electrodeposition growth rate for lateral PMC devices. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2020

Les travaux de recherche présentés dans ce mémoire, portent sur la conception et l’étude de MOSFETs de puissance faible tension pour des applications automobiles micro-hybrides de type alterno-démarreur. Pour certaines de ces applications, en plus des modes de fonctionnement standards passant et bloqué, les composants développés doivent être capables de fonctionner en mode d’avalanche à fort courant et à des températures élevées. Pour reproduire en laboratoire ces conditions de fonctionnement, les MOSFETs sont soumis à un test UIS répétitif spécifique. Afin d’évaluer la température du silicium pendant ce test, plusieurs méthodes de mesure de température ont été développées et comparées. En parallèle, un suivi des paramètres électriques standards (BVDSS, IDSS, RDSon…) tout au long du test est effectué, dans le but de déterminer l’impact de l’avalanche répétitive sur le transistor. Seule la RDSon des MOSFETs semble évoluer avec le nombre d’impulsions d’avalanche. Ce phénomène est expliqué par la méthode de mesure de RDSon et par la variation de la résistance du métal source pendant le cyclage. En effet, différentes observations ont permis de constater un vieillissement de la métallisation de source du composant, accompagné d’une modification de sa résistivité. Divers types de métaux et de techniques d’assemblage ont alors été expérimentés pour tenter de limiter cet effet. Aussi des structures de test ont été conçues pour étudier l’évolution du métal et pour pouvoir comparer rapidement le comportement de différentes métallisations / Research work presented in this thesis concern the conception and the study of low voltage power MOSFETs for micro hybrid vehicles (starter alternator). For some of these applications, developed transistors must be able to operate in classical ON and OFF state mode and in avalanche mode at high current and high temperature. To reproduce this operating mode, MOSFETs are submitted to a specific repetitive UIS test. In order to evaluate silicon’s temperature during this test, several temperature measurement methods have been developed and compared. In parallel, in order to understand the impact of repetitive avalanche on the transistor, standard electrical parameters (BVDSS, IDSS, RDSon…) are monitored during the test. The only parameter that seems to be shifting with the number of cycles is the RDSon. This phenomenon is due to the measurement method and to a variation of source metallization resistance during cycling. Indeed several observations have shown source metallization ageing and a shift in its resistivity. Different metallization and assembly parameters have been tested to limit this phenomenon. Also various test structures have been designed to study metallization evolution and to compare different metallization behaviors