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No. of bitstreams: 1 IgorOliveiraNascimento_TESE.pdf: 5575757 bytes, checksum: c19dabd04c4f5dd3dd95968e649af7af (MD5) Previous issue date: 2017-06-23 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / Filmes finos de nitreto de tit?nio foram depositados em superf?cies de sil?cio e de vidro, utilizando as t?cnicas de deposi??o: descarga em Gaiola Cat?dica e Magnetron Sputtering, a fim de verificar a influ?ncia da corrente e da temperatura na taxa de deposi??o, na estequiometria dos filmes finos e nas propriedades estruturais dos filmes finos. As deposi??es por Gaiola Cat?dica foram realizadas nas configura??es gaiola alta, gaiola baixa e por uma inova??o da t?cnica utilizando a gaiola dupla, em atmosfera gasosa composta de 75% de hidrog?nio e 25% de nitrog?nio, sob temperaturas de 300?C e 350?C, e tempos de deposi??es de 2 e 4 horas. As deposi??es foram realizadas em Magnetron Sputtering em atmosfera gasosa composta de 75% de arg?nio e 25% de nitrog?nio, utilizando correntes de 0,40 A e 0,50 A, nos tempos de deposi??es de 2 e 4 horas. Para a caracteriza??o dos filmes finos de nitreto de tit?nio, utilizou-se a espectroscopia Rama (RAMAN) que forneceu a medida direta das energias dos nodos da primeira ordem dos ?tomos constituintes dos filmes finos. Os espectros mostraram interdifusividade at?mica que comprovaram a forma??o de nitreto de tit?nio o que permitiu o c?lculo da raz?o da concentra??o N/Ti, As an?lises de difra??o de raios-X (DRX) comprovaram que os filmes finos obtidos s?o compostos por TiN, apresentando varia??es nos planos cristalinos indicando a n?o exist?ncia de um plano preferencial para o crescimento dos filmes, A espectroscopia de energia de dispers?o (EDS) analisou quantitativamente a composi??o dos filmes finos de nitreto de tit?nio, A microscopia eletr?nica de varredura (MEV) evidenciou a estrutura dos filmes finos de nitreto de tit?nio e foi poss?vel calcular as espessuras dos mesmos, A microscopia de for?a at?mica (AFM) mostrou algumas caracter?sticas microestruturais como a diferen?a entre picos e vales da topografia dos filmes finos de nitreto de tit?nio. De maneira geral, os filmes finos de nitreto de tit?nio depositados por Gaiola Cat?dica apresentaram menor cristalinidade devido ? baixa quantidade de nitrog?nio na atmosfera e, evidenciaram que quanto mais elevada a temperatura, maior ser? a espessura do filme fino. Os filmes finos depositados por Magnetron Sputtering apresentaram crescimento na espessura com o aumento da corrente e s?o mais estequiom?tricos. / Thin films of titanium nitride deposited on silicon surfaces and glass deposition techniques using: Download cathodic cage and Magnetron Sputtering to verify the influence of flow and temperature in the deposition rate in stoichiometry of thin films and structural properties of thin films. Deposits of cathodic cage was carried out in high cage configurations and cage low an innovation of the technique using atmospheric gas double cage consisted of 75% hydrogen and 25% nitrogen to temperatures of 300 ? C and 350 ? C Y deposits both 2 and 4 hours. The deposits were made in an atmosphere of sputter gas Magnetrons consisting of 75% argon and 25% nitrogen using current 0.40 A and 0.50 A in the deposition time of 2 and 4 hours. Rama spectroscopy (Raman), which makes available for the characterization of thin layers of titanium nitride direct measurement of the energy of the node of the first order of the constituent atom of the thin films. The spectra showed interdifusivity atomic of the titan nitride formation that the calculation of the concentration ratio N / Ti, X-ray diffraction analysis (XRD) showed that the thin films obtained from TiN is composite with variations of the crystal planes indicating the non-existence of preference plan for The growth of films, microscopy of the energy dispersion spectroscopy (EDS) quantitatively analysed the composition of the thin films of titanium nitride, electron scanning (MEV) structure highlight thin films of titanium nitride was able to calculate the thickness thereof, the scanning force microscopy (AFM) showed microstructural properties, Which is the difference between the peaks and valleys of the topography of the thin films of titanium nitride. In general, thin films deposited by cathodic titanium nitride cage deposited a lower crystallinity due to the small amount of nitrogen in the atmosphere, and showed that the higher the temperature, the greater the thickness of the thin film. Thin films deposited by Magnetron Sputtering have increased thickness with increasing current and are stoichiometric.

Lors de ce projet, des revêtements de CrN-WC ont été étudiés en temps que matériaux hybrides durs et résistants. L'association d'un carbure et d'un nitrure résistants bien à la corrosion et obtenus dans des conditions optimales de dépôt permettra d'avoir des matériaux de protection contre l'usure, la corrosion mais aussi des dépôts servant de couches tampon à du diamant nanocristallin dont l'adhérence est mauvaise. Tout d'abord nous avons déterminé la faisabilité du système de CrN-WC et son utilisation comme couche intermédiaire pour du diamant nanocristallin. En faisant varier les paramètres de dépôt, nous avons optimisé la microstructure, les caractéristiques chimiques, mécaniques et tribologiques de nos couches. Si le système CrN-WC adhère relativement bien sur silicium, ce ne fut pas le cas sur acier. Les propriétés mécaniques de ces dépôts ont été par ailleurs plus faibles que celles que nous attendions. Nous avons ensuite étudié l'influence de la température sur nos dépôts de CrN-WC. En effet, le fait de chauffer lors du dépôt permet d'augmenter l'adhérence des couches et d'améliorer leurs propriétés mécaniques. Les revêtements obtenus à haute température ont bien montré une amélioration marquée de leurs diverses caractéristiques par rapport aux dépôts obtenus sans chauff. / For this project, CrN-WC coatings are investigated as a hybrid hard and tough material. The use of a hard-carbide with a corrosion-resistant nitride may produce tailored coatings with the desired combination of properties for use as a stand-alone protective coating, or as a basis for nanocrystalline diamond deposition. The work is divided into three stages. The initial study determined the viability of the CrN-WC system, and its use as an interlayer for nanocrystalline diamond. This successful study was followed by a variation of deposition conditions at low deposition temperature. By varying the deposition parameters, the microstructure, chemical, mechanical, and tribological behavior may be optimized. While the system has relatively good adhesion to silicon substrates, its adhesion to steel was lacking. Additionally, the system showed lower than expected mechanical properties. The final step increased the deposition temperature. The aim here was to increase adhesion and improve the mechanical properties. Prior results with other systems show consistent improvement of mechanical properties at elevated deposition temperatures. The high deposition temperature coatings showed marked improvement in various characteristics over their low deposition temperature cousins.

Title: Study of 3-phase catalytic layers for polymer electrolyte fuel cells and electrolysers Author: Šimon Fuka Department: Department of Surface and Plasma Science Supervisor: doc. Mgr. Iva Matolínová, Dr., Department of Surface and Plasma Science Abstract: The diploma thesis focuses on the study of catalytic layers for Proton Exchange Membrane Fuel Cells (PEMFC) or electrolyzers based on the mixture of platinum and cerium oxide. These layers are prepared by using magnetron sputtering, their properties are studied depending on the deposition parameters or the choice of the substrate by using SEM, AFM, XPS and then tested as an anode in the fuel cell. In addition to the morphology of the catalytic layers, it has been shown that the dispersion of very small nanoparticles of the catalyst with a size of 1-2 nm has a great effect on PEMFC performance. Most of the prepared samples gave maximal and maximal specific performance much higher than the state of art values published for Pt-CeOx system. By studying properties of the layers used as the anode catalysts, this work contributes to the understanding of PEMFC fuel cell behavior and, consequently, to its potential commercialization. Keywords: Fuel cell, cerium oxide, platinum, catalyst, magnetron sputtering

Les films minces sont couramment employés pour apporter de nouvelles fonctionnalités au verre plat. Dans une grande gamme de produits industriels pour le bâtiment et l'automobile, l'isolation thermique est améliorée par le dépôt de films nanométriques d'Ag qui sont suffisamment minces pour la transparence optique mais suffisamment épais pour refléter l'infrarouge. Ces revêtements bas-emissifs sont des empilements complexes de films minces qui sont déposés à l'échelle industrielle par pulvérisation cathodique sur les panneaux de verre. Le démouillage ou la délamination peuvent réduire la performance optique et la durabilité du produit en raison de l'adhésion médiocre entre l'Ag et les couches adjacentes. Le film d'Ag est par conséquent pris en sandwich entre des couches texturées {0001} de ZnO qui se trouve être le meilleur candidat pour améliorer la cristallisation et l'adhésion. Des couches dites bloqueurs de métaux de transition tels que le Ti sont également ajoutées à l'interface. Dans ce cadre industriel, cette thèse s'est penchée sur divers aspects fondamentaux des interfaces métaux/ZnO en combinant des approches de science des surfaces sur des monocristaux et des films pulvérisés. Plusieurs stratégies de mesure et systèmes modèles ont été employés pour aborder les questions du contact électrique à l'interface Ag/ZnO, du contrôle de la polarité dans les films pulvérisés de ZnO et de l'évolution de la chimie à une interface enterrée Ti/ZnO lors d'un traitement thermique. / Thin films are a common way to add functionality to flat glass. In a wide range of commercial products for building materials and automotive industry, thermal insulation is improved by the deposition of a continuous nanometric film of Ag which is thin enough to ensure optical transparency but thick enough to reflect infra-red light. The low-emissive coatings consist of complex stacks of thin films deposited at the industrial scale by magnetron sputtering on window-sized glass plates. Dewetting or delamination may impact the performance and lifetime of the product due to a poor adhesion of Ag. Therefore, Ag is sandwiched in between ZnO{0001}-textured films which turned out to be the best candidate to improve Ag crystallization and adhesion. Blocker layers of transition metals, such as titanium, are also added at the interface. In this industrial context, the present thesis focused on several fundamental aspects of metal/ZnO interfaces by combining surface science approaches on single crystals and model sputtered films. Several original measurement strategies and model systems have been employed to tackle the questions of: (i) the Ag/ZnO electrical contact, (ii) the control of the polarity of sputtered ZnO films on amorphous substrates, and (iii) the evolution of the chemistry of buried Ti/ZnO interface during thermal treatment.

P-type transparent conductors are needed for a wide range of applicationssuch as solar cells and electrochromic smart windows. Solar power is animportant form of energy in today’s society as the threat of global warmingpushes the world towards fossil free energy. Hence a lot of solar cell typeshave been developed, among them tandem cells which are to different typesof solar cells stacked on top of each other. If one of the cells is based ona perovskite, a transparent p-type thin film electrode is needed as a holeconductor and electron blocking layer between the two cells. Nickel oxide(NiO) is a good candidate for this application as it has desired propertiessuch as good hole conduction, a high band gap and a matching work functionto the perovskite. The transmittance of as deposited NiO films by reactivemagnetron sputtered is limited so post deposition annealing is used to increasethe transmittance. This is not possible in this solar cell application as parts ofthe solar cell stack is temperature sensitive.Electrochromic smart windows contain a layer that can change its opticalproperties with the application of a voltage. Such windows are used inbuildings to increase energy efficiency and they contain an electrochromicdevice where NiO is used as an electrode as it has electrochromic properties,but just like with the solar cells, the transmittance of NiO is limited. Thisstudy investigates whether it is possible to make as deposited NiO by reactivemagnetron sputtering transparent, eliminating the need for post depositionannealing. Such a deposition process was found using different sputtermachines with the process point on the edge between metal and oxide modein terms of oxygen flow. This resulted in highly transparent and highlyresistive NiO films with a much higher deposition rate than in oxide mode.

Title: Study of new catalytic materials for proton exchange membrane fuel cells Author: Petr Homola Department: Department of Surface and Plasma Science Supervisor: Prof. RNDr. Vladimír Matolín, DrSc. Abstract: Submitted thesis deals with study of thin layers based on platinum and cerium oxides in order to use them in fuel cells with polymer membrane (PEM- FC). A set of samples with different amount of platinum was prepared by means of magnetron sputtering. Samples were investigated by X - ray Photoelectron Spectroscopy (XPS) and results were confronted with sputtering parameters. It was found out that chemical state of platinum is related to its amount in thin layer. The less platinum was contained in thin layer, the less amount of Pt0 state was observed and amounts of Pt2+ and Pt4+ states increased. Furthermore the temperature stability of prepared layers in the interval from room temperature to 250 ◦ C was studied by means of XPS. The adsorption of carbon monoxide was measured by infrared absorption spectroscopy (IRAS). Increasing degree of adsorption on sample probably related to platinum reduction with increased tem- perature was observed. Measurements of other samples were devaluated by strong contamination with nickel carbonyls. Keywords: PEMFC, cerium oxide, magnetron sputtering, XPS, CO adsorption

Presented work is focused on the deposition and characterization of thin and ultrathin plasma polymer films, then also on the preparation of nanocomposites metal/plasma polymer. The characterization of plasma polymer films was partly done in-situ without exposing the samples to the atmosphere. The thickness of prepared films was measured by spectral ellipsometry, the chemical composition was measured by XPS. The morphology and optical properties of deposited films were measured ex-situ. It is shown that during the initial stages of growth the properties of plasma polymer films depend on their thickness and also on the material of the substrate. Many interesting applications were explored for prepared nanocomposites metal/plasma polymer. They can be used as superhydrophobic coatings, gradient coatings, substrates for Raman spectroscopy or as antibacterial coatings. Moreover, special optical properties of prepared nanocomposites were studied in detail. Presented work has an experimental character.

The ball-pen probe is a unique probe recently developed at the Institite of Plasma Physics in Prague. It has been designed for direct measurement of plasma potential at the CASTOR tokamak. Nowadays, it is used routinely at several tokamaks in Europe, and the first tests in low-temperature plasma have also already been performed. The aims of the thesis are primarily experimental. A ball-pen probe has been constructed from available materials, which is suitable for systematic measurements of radial profiles in the low-temperature plasma of a cylindrical magnetron. By means of comparison to other diagnostics, it was proved that ball- pen probe is able to directly measure plasma potential in a certain range of plasma parameters even though its current-voltage characteristic is not symmetric, which is in contradiction with the simplified theory for ball-pen probe. Powered by TCPDF (www.tcpdf.org)

The goal of this work was to evaluate the electrochemical properties of TiZrNbTa thin films deposited by magnetron sputtering using an industrial physical vapor deposition system. Samples were deposited on both Si(001) and 316L stainless steel. The samples deposited on Si(001) were either crystalline (bcc reflections) or amorphous, depending on the sputtering parameters. The crystalline films were composed of thin films with two different layers. The upper layer was nanocolumnar composed of elongated nanocolumns, while the lower was dense. The amorphous films had only one nanocolumnar layer and higher porosity. Polarization curves revealed that all samples had low corrosion current densities, in the order of 10-8 A/cm2. The samples showed an extended passive region up to 3.0 V vs Ag/AgCl due to the growth of a passivating oxide. The surface of the samples consisted of Nb2O5, ZrO2, TiO2 and Ta2O5. The chronoamperometry tests showed current oscillations, related to a break-down and reformation of the passive film. Electrochemical impedance spectroscopy revealed that all samples behaved similarly in all three electrolytes, and the simulated electrical circuits were indicating no corrosion reactions. A decrease in capacitance values after polarization was observed and was related to the formed surface oxide. Samples deposited on 316L stainless steel showed a passive regime for a shorter potential window, probably related to surface defects of the films. Heat treatments at 400 and 800 Celsius for 20 hours could not trigger the phase transformation from single bcc to hcp or dual bcc, as predicted by the Thermo-Calc software.

In this thesis, growth of ZrB2 thin films by direct current magnetron sputtering is investigatedusing a high vacuum industrial scale deposition system and an ultra-high vacuum laboratory scalesystem. The films were grown from ZrB2 compound targets at temperatures ranging from ambient (without external heating) to 900 °C and with substrate biases from -20 to -120 V. Short deposition times of typically 100 or 300 s and high growth rates of 80-180 nm/min were emphasized to yield films with thicknesses of 300-400 nm. The films were characterized by thinfilm X-ray diffraction with the techniques θ/2θ and ω scans, pole figure measurements andreciprocal space mapping, scanning and transmission electron microscopy, elastic recoil detection analysis and four point probe measurements. The substrates applied were Si(100), Si(111),4H-SiC(0001) and GaN(0001) epilayers grown on 4H-SiC. The Si(111), 4H-SiC(0001) substrates and GaN(0001) epilayers were chosen given their small lattice mismatches to ZrB2 making them suitable for epitaxial growth.The films deposited in the industrial system were found to be close to stoichiometric with a low degree of contaminants, with O being the most abundant at a level of < 1 at.%. Furthermore, the structure of the films is temperature dependent as films deposited in this system without external heating are fiber textured with a 0001-orientation while the films deposited at 550 °C exhibitrandom orientation. In contrast, epitaxial growth was demonstrated in the laboratory scale system on etched 4H-SiC(0001) and Si(111) deposited at 900 °C following outgassing of the substrates at 300 °C and in-situ heat treatment at the applied growth temperature to remove the native oxides. However, films grown on GaN(0001) were found to be 0001 textured at the applied deposition conditions, which make further studies necessary to enable epitaxial growth on this substrate material. Four point probe measurements on the films deposited in the industrial system show typical resistivity values ranging from ˜95 to 200 μΩcm with a trend to lower values for the films deposited at higher temperatures and at higher substrate bias voltages.