Bipolar electrochemistry is an interesting concept for high throughput screening techniques due to the ability to induce gradients in a range of materials and their properties, such as composition, particle size, or dopant levels, among many others. One of the key advantages of the method is the ability to test, create or modify materials without the need for a direct electrical connection. In this thesis, the viability of this method has been explored for a range of possible applications, such as metal recycling, nanoparticle modification and corrosion analysis. In the initial part of the work a process to electrodeposit gradients in metal composition was evaluated, with a view to applying the technique to the extraction and recycling of metals from fly ash. Compositional gradients in the metals under study could be readily obtained from controlled reference solutions, although the spatial resolution of the metals was not sufficient to perform separation. Only copper could be easily deposited from the fly ash solution. Bipolar electrodeposition was also successfully used to modify the particle size across substrates decorated with gold nanoparticles. The approach was demonstrated both for surfaces possessing either a uniform particle density or a gradient in particle density. In the latter case samples with simultaneous, orthogonal gradients in both particle size and density were obtained. A combination of the bipolar approach with rapid image analysis was also evaluated as a method for corrosion screening, using quantitative analysis of gradients in pitting corrosion damage on stainless steels in HCl as a model system. The factors affecting gradient formation and the initiation of corrosion were thoroughly investigated by the use of a scanning droplet cell (SDC) technique and hard x-ray photoelectron spectroscopy (HAXPES). The ability to screen arrays of different materials for corrosion properties was also investigated, and demonstrated for stainless steel and Ti-Al alloys with pre-formed compositional gradients. The technique shows much promise for further studies and for high throughput corrosion screening applications.

Doppelt diffusive Konvektion im Fingerregime wurde mittels einer elektrochemischen Zelle untersucht. Kupferionen bilden die destabilisierende und Temperatur die stabilisierende Komponente. In diesen System existieren Finger und thermohaline Treppen, obwohl die Gesamtdichtestratifizierung instabil ist. Fingerströmung wird durch Konvektionsrollen ersetzt, wenn die Konvektion schnell genug ist um Temperaturdiffusion zwischen den Fingern zu unterbinden, bzw. wenn die thermische Auftriebskraft 1/30 der chemischen Auftriebskraft beträgt. Am Übergang ist der Ionentransport größer, als ohne stabilisierenden Temperaturgradienten.

Nanocrystalline cerium oxide thin films on metal and semiconductor substrates have been fabricated with a novel electrodeposition approach - anodic oxidation. X-ray diffraction analysis indicated that as-produced cerium oxide films are characteristic face-centered cubic fluorite structure with 5 ~ 20 nm crystal sizes. X-ray photoelectron spectroscopy study probes the non-stoichiometry property of as-produced films. Raman spectroscopy and Scanning Electron Microscopy have been applied to analyze the films as well. Deposition mode, current density, reaction temperature and pH have also been investigated and the deposition condition has been optimized for preferred oriented film formation: galvanostatic deposition with current density of -0.06 mA/cm2, T > 50oC and 7 < pH < 10. Generally, potentiostatic deposition results in random structured cerium oxide films. Sintering of potentiostatic deposited cerium oxide films leads to crystal growth and reach nearly full density at 1100oC. It is demonstrated that in-air heating favors the 1:2 stoichiometry of CeO2. Nanocrystalline cerium oxide powders (4 ~ 10 nm) have been produced with anodic electrochemical synthesis. X-ray diffraction and Raman spectroscopy were employed to investigate lattice expansion phenomenon related to the nanoscale cerium oxide particles. The pH of reaction solution plays an important role in electrochemical synthesis of cerium oxide films and powder. Cyclic voltammetry and rotation disk electrode voltammetry have been used to study the reaction mechanisms. The results indicate that the film deposition and powder formation follow different reaction schemes. Ce(III)-L complexation is a reversible process, Ce3+ at medium basic pH region (7~10) is electrochemically oxidized to and then CeO2 film is deposited on the substrate. CE mechanism is suggested to be involved in the formation of films, free Ce3+ species is coordinated with OH- at high basic pH region (>10) to Ce2O3 immediately prior to electrochemically oxidation Ce2O3 to CeO2. CeO2 / montmorillonite nanocomposites were electrochemically produced. X-ray diffraction and Raman spectroscopy illustrate the retaining of FCC structure for cerium oxide. Fourier Transform Infrared Spectroscopy and Differential Scanning Calorimetry of composites indicate the insertion of montmorillonite platelets into the structural matrix of cerium oxide. Sintering study of the nanocomposites demonstrates that low concentration of montmorillonite platelet coordination into cerium oxide matrix increases crystal growth rate whereas high concentration of montmoillonite in nanocomposites retards the increase of crystallite size during the densification process.

The optimal conditions for deposition of zinc-nickel alloys onto stainless steel discs in alkaline solutions have been examined. In the past cadmium has been used because it shows good corrosion protection, but other methods are being examined due to the high toxicity and environmental threats posed by its use. Zinc has been found to provide good corrosion resistance, but the corrosion resistance is greatly increased when alloyed with nickel. The concentration of nickel in the deposit has long been a debated issue, but for basic solutions a nickel concentration of 8-15% appears optimal. However, deposition of zinc-nickel alloys from acidic solutions has average nickel concentrations of 12-15%. Alkaline conditions give a more uniform deposition layer, or better metal distribution, thereby a better corrosion resistance. Although TEA (triethanolamine) is most commonly used to complex the metals in solution, in this work I examined TEA along with other complexing agents. Although alkaline solutions have been examined, most research has been done in pH &#8805; 12 solutions. However, there has been some work performed in the pH 9.3-9.5 range. This work examines different ligands in a pH 9.3-9.4 range. Direct potential plating and pulse potential plating methods are examined for optimal platings. The deposits were examined and characterized by XRD.

L’électrochimie bipolaire est un phénomène générant une réactivité asymétrique à la surface d’objets conducteurs, sans contact électrique direct. Ce concept est basé sur le fait que lorsqu’un objet conducteur est localisé dans un champ électrique, il se polarise. Par conséquent, une différence de potentiel est générée entre ses deux extrémités, et peut être utilisée pour induire des réactions redox localisées. Dans cette thèse, l’utilisation de l’électrochimie bipolaire pour la science des matériaux et pour la locomotion d’objets est présentée.Jusqu’à présent, la plupart des méthodes ou procédés utilisés pour générer des objets asymétriques,appelés aussi objets « Janus », nécessitent l’introduction d’une interface pour briser la symétrie. Nous avons développé une nouvelle approche basée sur l’électrodéposition bipolaire pour générerce type d’objet en grande quantité. Grâce à cette technologie différents matériaux tels que des métaux, des polymères et des semi‐conducteurs ont pu être déposés sur diverses particulesconductrices. Il a été aussi démontré que l’électrochimie bipolaire pouvait être utilisée pour lamicrostructuration de substrats conducteurs.Nous avons induit des mouvements à des objets conducteurs en exploitant le phénomèned’électrochimie bipolaire. Certains objets Janus synthétisés par l’approche précédente ont pu être utilisés comme micronageurs. La brisure de symétrie qui est générée par l’électrochimie bipolaire peut être aussi utilisée directement pour générer un mouvement de particules isotropes. En employant ce concept, nous avons pu provoquer des mouvements de translation, rotation et lévitation pour des particules de carbones ou métalliques. / The phenomenon of bipolar electrochemistry generates an asymmetric reactivity on the surface ofconductive objects in a wireless manner. This concept is based on the fact that when a conducingobject is placed in an electric field, it gets polarized. Consequently, a potential difference appearsbetween its two extremities, that can be used to drive localized redox reactions. In the presentthesis, bipolar electrochemistry was used for material science and the locomotion of objects.So far, the majority of methods and processes used for the generation of asymmetric objects, alsocalled “Janus” objects, is based on using interfaces to break the symmetry. We developed a newapproach based on bipolar electrodeposition for generating this type of objects in the bulk. Using thistechnology, various materials like metals, polymers and semiconductors could be deposited ondifferent types of conducting particles. We also showed that bipolar electrochemistry can be used forthe microstructuration of conducting substrates.Motion generation by bipolar electrochemistry has also been demonstrated. Some of the Janusobjects synthesized by the previous approach can be used as microswimmers. The asymmetricreactivity that is induced by bipolar electrochemistry can also be used directly to generate motion ofnon‐hybrid objects. With this concept we induced translations, rotations and levitations of carbonand metal particles.

The demand for alternative secondary batteries to lithium-ion batteries (LIBs) grows. Sodium-ion batteries (SIBs) have been studied for many years and could replace LIBsfor some application. Metallic anodes for both LIBs and SIBs are interesting due totheir high energy densities. Several aspects such as reactivity, stability and depositionmorphology must be properly addressed before metallic Na could be considered apossible anode material. This study aims to evaluate deposition of Na on Alelectrodes using fundamental electrochemical theories. Na deposition was studiedusing pouch cells and sodium triflate (NaOTf) in dimethyl glycol ether (diglyme) aselectrolyte. Galvanostatic deposition using different current densities, electrolyteconcentrations and potential pulses prior to galvanostatic deposition were tested. Theelectrochemical methods used in this study were galvanostatic deposition andchronoamperometry. The morphology of deposited Na was analyzed with ex-situscanning electron microscopy (SEM). A decrease of the size of deposited Na islandswas observed for both increasing current density and decreasing electrolyteconcentration. Fluctuations and poor stability in the deposition potential wereobtained when decreasing the electrolyte concentration under 0.5 M and also whenincreasing the current density over 1 mA cm-2. The most homogeneous depositionwas obtained with a 1030 ms potential pulse amplitude (-3 V vs. Na+/Na) prior togalvanostatic deposition (1 mA cm-2, 0.5 mAh cm-2) using 0.1 M NaOTf in diglyme aselectrolyte. Reproducibility was a major issue in this study and further investigation ofseveral parameters is needed.

Interfases Cu/NaOH e Pt/NaOH foram estudadas a 25 oC, a várias concentrações de NaOH, 1,0 x10-3 mol.L-1 a 5,0 mol.L-1, empregando técnicas eletroquímicas e não eletroquímicas na ausência e presença do íon acrilato. Os estudos tiveram como objetivo obter informações sobre a dupla camada elétrica (DCE) e sobre a reação H2O/H2 empregando cobre como substrato, para um melhor entendimento da eletrodeposição do gálio. Os estudos foram precedidos de ensaios tecnológicos em que as condições experimentais e a natureza dos sistemas a serem estudados foram estabelecidas. Estudos por voltametria cíclica provaram que em NaOH 5,0 mol.L-1 os processos de oxidação e redução do cobre são qualitativamente semelhantes aos observados em NaOH 0,1 mol.L-1, mas a velocidade destes processos se torna uma ordem de grandeza maior em NaOH 5,0 mol.L-1. Ensaios por voltametria linear indicaram que a redução dos óxidos na superfície e a menor pureza do cobre (99,99% comparado a 99,999 %) elevam a velocidade da reação H2O/H2. Estudos cronoamperométricos mostraram a viabilidade do emprego desta técnica nos estudos da DCE da interfase Cu/NaOH 5,0 mol.L-1 na região de potencial em que os processos faradaicos são da ordem de 20 microA.cm-2 em condições estacionárias. As interfases Cu/NaOH foram comparadas com as interfases Pt/NaOH e os resultados obtidos por cronoamperometria, para platina, foram comparados com os observados por espectroscopia de impedância eletroquímica (EIE). O valor de -158 mV/(Hg/HgO) para o potencial de carga zero, determinado por EIE é comparável ao obtido por cronoamperometria (-125 mV/ Hg/HgO), mantidos constantes os tratamentos superficiais do eletrodo e a pureza das soluções. A aplicação do modelo de Gouy Chapman para a solução diluída (10-3 mol.L-1), no potencial de carga zero, permitiu avaliar, conhecida a capacitância da DCE, os valores de capacitância. C1, no plano interno de Helmholtz. A partir de C1 foi possível calcular a constante dielétrica, , nesta região, encontrando-se por EIE o valor = 13,1. A aplicação do modelo de Helmholtz às soluções de NaOH 5,0 mol.L-1 permitiu determinar por cronoamperometria, a constante dielétrica na interfase, tanto para Cu/NaOH 5,0 mol.L-1 (igual a 44), quanto para Pt/NaOH 5,0 mol.L-1(igual a 25). O emprego da microbalança de cristal de quartzo permitiu verificar a adsorção do íon acrilato desde o potencial de circuito aberto. O ion acrilato inibe todos os processos que ocorrem sobre platina (entre 0,4 V/(Hg/HgO) e -1,0 V(Hg/HgO)) e sobre cobre (entre -0,8 V(Hg/HgO) e -1,6 V(Hg/HgO)). Estudos potenciostáticos sob condições estacionárias mostraram que o acrilato inibe a deposição do gálio sobre cobre em meio de NaOH 5,0 mol.L-1, o que foi verificado por técnicas de microscopia eletrônica de varredura (MEV) e energia dispersiva de raios-X (EDS). Os resultados evidenciaram que o cuidado no emprego do acrilato no processamento da alumina deve ser levado em conta, quando se deseja obter gálio metálico como subproduto. / Cu/NaOH and Pt/NaOH interphases have been studied at 25oC, in a concentration range of 1.0 x 10-3 mol.L-1 to 5.0 mol.L-1, using electrochemical and non-electrochemical techniques in the absence and in the presence of acrylate ions. The main goal of this study was to obtain information about the electrical double layer (EDL) and about the reaction H2O/H2 using copper as substract, in order to have a better understanding of gallium electrodeposition. The experimental conditions and the nature of the systems have been defined by technological researches performed previously to these experiments. Cyclic voltammetric studies have proved that both oxidation and reduction processes of copper in NaOH 5.0 mol.L-1 are qualitatively similar to those observed in 0.1 mol.L-1 but the reaction rate is one order of magnitude higher than in 0.1. mol.L-1. Linear voltammetric experiments have pointed out that the reaction rate of H2O/H2 is increased with the decrease in copper purity (99,99% compared to 99,999%) and with the reduction of the oxides on the surface. Chronoamperometric studies have shown its viability on the study of EDL corresponding to Cu/NaOH interphase on the potential region where the faradaic processes are of the order of magnitude of 20 microA.cm-2 under stationary conditions. Cu/NaOH interphases have been compared to Pt/NaOH interphases and the chronoamperometric results obtained for platinum have been compared to those observed by electrochemical impedance spectroscopy (EIS). The value of -158 mV/(Hg/HgO) for the zero charge potential calculated by EIS is comparable to the one obtained by chronoamperometry (-125 mV/Hg/HgO) maintaining constants both the electrode surface treatment and the purity of the solutions. The application of the Gouy Chapman model for the more dilute solution (10-3 mol.L-1) at zero charge potential (knowing the EDL capacitance), allowed to evaluate the capacitance values of the Helmholtz internal plane C1. Knowing C1, it was possible to calculate the dielectric constant ( ) in this region by EIS ( = 13.1). The application of the Helmholtz model to NaOH 5.0 mol.L-1 solutions allowed to calculate the dielectric constant on the interphase by chronoamperometry for both Cu/NaOH 5.0 mol.L-1 ( = 44) and Pt/NaOH 5.0 mol.L-1 ( = 25) interphases. The use of electrochemical quartz crystal microbalance permitted to verify the adsorption of acrylate ion from the open circuit potential. Acrylate ion inhibits all the processes that occur over both platinum (from 0.4 V/Hg/HgO to -1.0 V/Hg/HgO) and copper (from -0.8 V/Hg/HgO to -1.6 V/Hg/HgO). Potentiostatic studies over stationary conditions have shown that acrylate ion inhibits the gallium deposition on copper in 5.0 mol.L-1 medium, which is in agreement with what is observed by scanning electron microscopy (SEM) and energy dispersion spectroscopy (EDS). The results point out that care must be taken when using acrylate on alumina processing if gallium metallic is intended as subproduct.

A presente tese trata da simulação computacional dos estágios iniciais da eletrodeposição de cobalto sobre carbono e de cobre sobre ouro, utilizando o método de Monte Carlo Cinético. Os fenômenos de adsorção, dessorção, deposição e difusão superficial, entre outros, ocorrem simultânea e independentemente durante a eletrodeposição, em função de certa probabilidade. Sorteios aleatórios dos eventos de acordo com essa distribuição de probabilidades simulam o comportamento real complexo de um sistema durante a eletrodeposição. No caso do cobalto, foi utilizada uma descrição teórica detalhada das interações entre os átomos no sistema, que permitiu que fossem observadas as formações dos primeiros núcleos, a predileção pela eletrodeposição nos defeitos superficiais e os distintos mecanismos dependentes do sobrepotencial elétrico aplicado. No caso do cobre, foi utilizada uma descrição empírica mais simples da interação entre os átomos, o que permitiu que a quantidade de espécies simuladas fosse maior e aspectos relacionados ao crescimento do filme metálico fossem obtidos, tais quais a formação de buracos durante o processo e a obtenção de parâmetros importantes, como tamanho, altura e densidade média dos núcleos. Alguns experimentos foram realizados para fundamentar e complementar o estudo teórico / This thesis reports the computer simulation of the first stages of the electrodeposition of cobalt onto carbon and copper onto gold, using the Kinetic Monte Carlo method. Adsorption, desorption, deposition and surface diffusion, among other events, occur simultaneously and independently during the electrodeposition, according to a given probability. Random choices of events as a result of a probability distribution can simulate the real evolution of a complex system during the electrodeposition. Regarding the cobalt system, a detailed theoretical interatomic description was used, which allowed the observance of the formation of the first nuclei, the preference of the electrodeposition on the surface defects and the deposition mechanisms differences depending on the applied overpotential. Regarding copper, a much simpler, empiric-based interatomic description was used, allowing the simulation of a bigger number of particles. Some features regarding the copper film growth (like the formation of voids during the process) and some important deposition parameters (like the average size, height and density of the nuclei) were obtained. Some experiments were held in order to base and complement the theoretical study

Grâce à des propriétés physiques spécifiques différentes des matériaux massifs, les nanostructures ont mené à une rupture technologique importante. Le silicium étant le matériau prédominant en microélectronique, et du fait d’un rapport surface/volume important, les nanofils de silicium sont prometteurs dans de nombreux domaines d’applications comme l’optoélectronique ou les capteurs biologiques. Néanmoins les techniques de synthèse actuellement utilisées sont encore relativement complexes à mettre en œuvre et coûteuses et il existe encore un écart énorme entre la synthèse et la mise au point de démonstrateurs en laboratoire et la réalisation de dispositifs fonctionnels et commercialisables.Ce travail de thèse porte sur l’étude d’une nouvelle technique de synthèse bas coût, l’électrodépôt en liquide ionique, pour obtenir des nanofils de silicium ou de silicium incorporant des ions Terre-Rare avec des propriétés d’émission dans le visible ou le proche infrarouge. Un des objectifs de cette thèse étaient de comprendre l’influence des différents paramètres d’électrodépôt sur la croissance de films minces de silicium pur et de voir si il était possible de synthétiser par cette voie des films Silicium/terbium, le terbium émettant dans le visible, et Silicium/Erbium, l’erbium émettant à 1,55 µm. Grâce aux études électrochimiques et aux caractérisations structurales des films minces, nous avons montré que ce mode de synthèse permettait d’obtenir des films minces de silicium amorphe de très bonne qualité et sans impureté avec une croissance laminaire. En jouant sur le potentiel de dépôt, la température et la concentration en espèces actives, nous avons pu maîtriser et optimiser les conditions de croissance, ce qui nous a permis ensuite d’obtenir des nanofils de silicium amorphe avec des diamètres allant de quelques dizaines à quelques centaines de nanomètres en utilisant des membranes nanoporeuses comme moule. Ces nanofils sont passivés par une couche d’oxyde de surface après dissolution de la membrane et remise à l’air. Une propriété intéressante de ces nanofils de silicium amorphe est qu’ils possèdent une forte luminescence dans le rouge à température ambiante, en particulier pour des diamètres de l’ordre de 100 nm. Des études optiques et structurales ont permis de montrer que cette émission provenait du caractère amorphe des nanofils et qu’un mécanisme de recombinaison entre queues de bande et le confinement spatial des porteurs dans les nanofils permettait d’expliquer l’émission intense observéeLa 2ème partie importante de la thèse portait sur la possibilité de réaliser des films et des nanofils de type silicium / terres rares. Nous avons montré pour la 1ère fois, qu’il était de synthétiser des co-dépôts simultanés de silicium et d’éléments de terre rare pour le Tb et l’Er sous forme de films minces. En faisant varier le potentiel de dépôt, nous avons mis en évidence qu’il était possible de faire varier la concentration de terre-rare incorporée de quelques % à 20%. Les études structurales montrent que cette incorporation se fait de façon homogène dans l’épaisseur des films et sans changer la morphologie. Grâce à cette homogénéité, les films minces obtenus émettent à température ambiante et aux longueurs d’onde attendues pour les ions terre-rare. Suite à cette étude sous forme de films minces, nous avons ensuite réalisé la croissance de nanofils Si/Tb et Si/Er en utilisant des membranes nanoporeuses. Nous avons obtenu des nanofils de silicium incorporant du terbium ou de l’erbium avec des concentrations pouvant varier. Les nanofils ainsi synthétisés sont également homogènes en composition sur toute la longueur et émettent avec des fortes intensités à température ambiante pour le terbium. Pour les nanofils Si/Er, l’intensité d’émission est faible à température ambiante mais un recuit thermique permet d’activer les ions terbium et d’obtenir une émission intense à température ambiante. / Thanks to their specific physical properties different from the massive materials, nanostructured materials have led to important technological progress. Since silicon is the predominant material in microelectronics, and due to a large surface to volume ratio, silicon nanowires are promising in many fields of applications such as optoelectronics or biological sensors. Nevertheless, the synthesis techniques currently used are still relatively complex to implement and thus costly and there is still a huge gap between the synthesis and the development of laboratory demonstrators and the realization of functional and marketable devices.This thesis work deals with the study of a new low cost synthesis technique, the electrodeposition in ionic liquid, to grow nanowires of silicon or silicon incorporating Earth-Rare ions with emission properties of emission in the visible or the near infrared range. One of the objectives of this thesis was to understand the influence of the different electrodeposition parameters on the growth of pure silicon thin films and to see if it was possible to synthesize silicon/terbium films, the terbium emitting in the visible, and Silicon/Erbium, erbium emitting at 1.55 μm. Thanks to different electrochemical studies and structural characterization of thin films, we have shown that this mode of synthesis makes it possible to obtain thin films of amorphous silicon of very good quality and without impurity. By controlling the deposition potential, temperature, and active species concentration, we were able to control and optimize the growth conditions, which allowed us to obtain amorphous silicon nanowires with diameters ranging from a few tens to a few hundred nanometers using nanoporous membranes as a mold. These nanowires are passivated by a surface oxide layer after dissolution of the membrane and exposition to air. An interesting property of these amorphous silicon nanowires is that they have a high luminescence in the red range at room temperature, in particular for diameters in the order of 100 nm. Optical and structural studies showed that this emission was due to the amorphous nature of the nanowires and that a mechanism of band-tail recombination and the spatial confinement of the carriers whitin the nanowires made it possible to explain the intense emission observed.The second important part of the thesis was the possibility of making films and nanowires of the silicon/rare earth type. We have shown for the first time that it was possible to synthesize simultaneous co-deposited films of silicon and rare earth elements for Tb and Er. By varying the deposition potential, we have shown that it is possible to tune the incorporated rare earth concentration by a few % to 20%. The structural studies show that this incorporation is carried out homogeneously in the thickness of the films and without changing the morphology. Thanks to this homogeneity, the thin films obtained emit at ambient temperature and at the expected wavelengths for the rare earth ions. Following this study as thin films, we then carried out the growth of Si/Tb and Si/Er nanowires using nanoporous membranes. We have obtained nanowires of silicon incorporating terbium or erbium with varying concentrations. The nanowires thus synthesized are also homogeneous in composition over the entire length and emit with high intensities at ambient temperature for terbium. For Si/Er nanowires, the emission intensity is low at ambient temperature but thermal annealing makes it possible to activate the terbium ions and to obtain an intense emission at ambient temperature.

A presente tese trata da simulação computacional dos estágios iniciais da eletrodeposição de cobalto sobre carbono e de cobre sobre ouro, utilizando o método de Monte Carlo Cinético. Os fenômenos de adsorção, dessorção, deposição e difusão superficial, entre outros, ocorrem simultânea e independentemente durante a eletrodeposição, em função de certa probabilidade. Sorteios aleatórios dos eventos de acordo com essa distribuição de probabilidades simulam o comportamento real complexo de um sistema durante a eletrodeposição. No caso do cobalto, foi utilizada uma descrição teórica detalhada das interações entre os átomos no sistema, que permitiu que fossem observadas as formações dos primeiros núcleos, a predileção pela eletrodeposição nos defeitos superficiais e os distintos mecanismos dependentes do sobrepotencial elétrico aplicado. No caso do cobre, foi utilizada uma descrição empírica mais simples da interação entre os átomos, o que permitiu que a quantidade de espécies simuladas fosse maior e aspectos relacionados ao crescimento do filme metálico fossem obtidos, tais quais a formação de buracos durante o processo e a obtenção de parâmetros importantes, como tamanho, altura e densidade média dos núcleos. Alguns experimentos foram realizados para fundamentar e complementar o estudo teórico / This thesis reports the computer simulation of the first stages of the electrodeposition of cobalt onto carbon and copper onto gold, using the Kinetic Monte Carlo method. Adsorption, desorption, deposition and surface diffusion, among other events, occur simultaneously and independently during the electrodeposition, according to a given probability. Random choices of events as a result of a probability distribution can simulate the real evolution of a complex system during the electrodeposition. Regarding the cobalt system, a detailed theoretical interatomic description was used, which allowed the observance of the formation of the first nuclei, the preference of the electrodeposition on the surface defects and the deposition mechanisms differences depending on the applied overpotential. Regarding copper, a much simpler, empiric-based interatomic description was used, allowing the simulation of a bigger number of particles. Some features regarding the copper film growth (like the formation of voids during the process) and some important deposition parameters (like the average size, height and density of the nuclei) were obtained. Some experiments were held in order to base and complement the theoretical study