<p>Ferroelectrics are a group of advanced electronic materialswith a wide variety of properties useful in applications suchas memory devices, resonators and filters, infrared sensors,microelectromechanical systems, and optical waveguides andmodulators. Among the oxide perovskite-structured ferroelectricthin film materials sodium potassium niobate or Na0.5K0.5NbO3(NKN) has recently emerged as one of the most promisingmaterials in microwave applications due to high dielectrictunability and low dielectric loss. This licentiate thesispresents results on growth and structural, optical, andelectrical characterization of Na0.5K0.5NbO3 thin films. Thefilms were deposited by rf-magnetron sputtering of astoichiometric, high density, ceramic Na0.5K0.5NbO3 target ontosingle crystal LaAlO3 and Al2O3, and polycrystalline Pt80Ir20substrates. By x-ray diffractometry, NKN films on c-axisoriented LaAlO3 substrates were found to grow epitaxially,whereas films on hexagonal sapphire and polycrystallinePt80Ir20 substrates were found to be preferentially (00l)oriented. Optical and waveguiding properties of theNa0.5K0.5NbO3/Al2O3 heterostructure were characterized using aprism-coupling technique. Sharp and distinguishable transversemagnetic (TM) and electric (TE) propagation modes wereobserved. The extraordinary and ordinary refractive indiceswere calculated to ne = 2.216±0.003 and no =2.247±0.002 for a 2.0 μm thick film at λ = 632.8nm. This implies a birefringence Δn = ne - no =-0.031±0.003 in the film. The ferroelectric state inNKN/Pt80Ir20 films at room temperature was indicated by apolarization loop with polarization as high as 33.4 μC/cm2at 700 kV/cm, remnant polarization of 9.9 μC/cm2 andcoercive field of 91 kV/cm. Current-voltage characteristics ofvertical Au/NKN/Pt80Ir20 capacitive cells and planar Au/NKN/LaAlO3 interdigital capacitors (IDCs) showed very goodinsulating properties, with the leakage current density for anNKN IDC on the order of 30 nA/cm2 at 400 kV/cm. Rf dielectricspectroscopy demonstrated low loss, low frequency dispersion,and high voltage tunability. At 1 MHz NKN/LaAlO3 showed adissipation factor tan δ of 0.010 and a tunability of 16.5% at 200 kV/cm. For the same structure the frequencydispersion, Δεr, between 1 kHz and 1 MHz was 8.5%.</p><p><b>Key words:</b>ferroelectrics, sodium potassium niobates,thin films, rf-magnetron sputtering, waveguiding, refractiveindex, prism coupling, dielectric tunability</p>

The present thesis addresses two research areas related to film growth in a highly ionized magnetron sputtering system: plasma characterization, and thin film growth and analysis. The deposition technique used is called high power pulsed magnetron sputtering (HPPMS). Characteristic for this technique are high energy pulses (a few Joules) of length 50-100 µs that are applied to the target (cathode) with a duty time of less than 1 % of the total pulse time. This results in a high electron density in the discharge (&gt;1x1019 m-3) and leads to an increase of the ionization fraction of the sputtered material reaching up to 70 % for Cu. In this work the spatial and temporal evolution of the plasma parameters, including the electron energy distribution function (EEDF), the electron density and the electron temperature are determined using electrostatic Langmuir probes. Electron temperature measurements reveal a low effective temperature of 2-3 eV. The degree of ionization in the HPPMS discharge is explained in light of the self-sputtering yield of the target material. A simple model is therefore provided in order to compare the sputtering yield in HPPMS and that in dc magnetron sputtering (dcMS) for the same average power. Thin Ta films are grown using HPPMS and dcMS and their properties are studied. It is shown that enhanced microstructure and morphology of the deposited films is achieved by HPPMS. The Ta films are also deposited at a number of substrate inclination angles ranging from 0o (i.e., facing the target surface) up to 180 o (i.e., facing away from the target). Deposition rate measurements performed at all inclination angles for both techniques, reveal that growth made using HPPMS resulted in an improved film thickness at higher inclination. Furthermore, the high ionization of the Ta atoms in HPPMS discharge is found to allow for phase tailoring of the deposited films at all inclination angles by applying a bias voltage to the substrate. Finally, highly ionized magnetron sputtering of a compound MAX-phase material (Ti3SiC2) is performed, demonstrating that the HPPMS discharge could also be used to tailor the composition of the growing Ti-Si-C films. / On the day of the public defence of the doctoral thesis, the status of articles III and IV was Submitted. The titles of papers VI and VII changed between their manuscript forms and when they were published.

In plasma assisted thin film growth, control over the energy and direction of the incoming species is desired. If the growth species are ionized this can be achieved by the use of a substrate bias or a magnetic field. Ions may be accelerated by an applied potential, whereas neutral particles may not. Thin films grown by ionized physical vapor deposition (I-PVD) have lately shown promising results regarding film structure and adhesion. High power impulse magnetron sputtering (HIPIMS) is a relatively newly developed technique, which relies on the creation of a dense plasma in front of the sputtering target to produce a large fraction of ions of the sputtered material. In HIPIMS, high power pulses with a length of ~100 μs are applied to a conventional planar magnetron. The highly energetic nature of the discharge, which involves power densities of several kW/cm2, creates a dense plasma in front of the target, which allows for a large fraction of the sputtered material to be ionized. The work presented in this thesis involves plasma analysis using electrostatic probes, optical emission spectroscopy (OES), magnetic probes, energy resolved mass spectrometry, and other fundamental observation techniques. These techniques used together are powerful plasma analysis tools, and used together give a good overview of the plasma properties is achieved. from the erosion zone of the magnetron. The peak plasma density during the active cycle of the discharge exceeds 1019 electrons/m3. The expanding plasma is reflected by the chamber wall back into the center part of the chamber, resulting in a second density peak several hundreds of μs after the pulse is turned off. Optical emission spectroscopy (OES) measurements of the plasma indicate that the degree of ionization of sputtered Ti is very high, over 90 % in the peak of the pulse. Even at relatively low applied target power (~200 W/cm2 peak power) the recorded spectrum is totally dominated by radiation from ions. The recorded HIPIMS spectra were compared to a spectrum taken from a DC magnetron discharge, showing a completely different appearance. Magnetic field measurements performed with a coil type probe show significant deformation in the magnetic field of the magnetrons during the pulse. Spatially resolved measurements show evidence of a dense azimuthally E×B drifting current. Circulating currents mainly flow within 2 away cm from the target surface in an early part of the pulse, to later diffuse axially into the chamber and decrease in intensity. We record peak current densities of the E×B drift to be of the order of 105 A/m2. A mass spectrometry (MS) study of the plasma reveals that the HIPIMS discharge contains a larger fraction of highly energetic ions as compared to the continuous DC discharge. Especially ions of the target material are more energetic. Time resolved studies show broad distributions of ion energies in the early stage of the discharge, which quickly narrows down after pulse switch-off. Ti ions with energies up to 100 eV are detected. The time average plasma contains mainly low energy Ar ions, but during the active phase of the discharge, the plasma is highly metallic. Shortly after pulse switch-on, the peak value of the Ti1+/Ar1+ ratio is over 2. The HIPIMS discharge also contains a significant amount of doubly charged ions.

The theoretical part deals with basic characteristics of low-temperature, low-pressure plasma. It also describes the principles of preparation of polymer and nanocomposite films using this type of plasma. It further explains the basic principles of methods used to characterize our samples. The experimental section shows a technology to produce hard polymeric coatings with metal (Cu) nanoparticles (NPs) fabricated by gas aggregation source (GAS). This approach has an important advantage that Cu concentration and matrix properties can be controlled independently. Characterization of the films in terms of chemical composition, morphology, optical and mechanical properties is described here alongside with description of Cu NPs production using GAS with variable aggregation length. The a- C:H matrix was deposited in a mixture of Ar and n-hexane on the substrates placed on a RF electrode. The beam of the NPs was normal to the substrate plane. In this arrangement it was possible to control hardness of the films and by operational parameters of the GAS also the amount of the NPs in the film. In the last section fabrication of nanocomposite films of titanium and nylon NPs is shown. Powered by TCPDF (www.tcpdf.org)

Le but de ce travail est de développer et de caractériser une nouvelle génération de revêtements multicouches anti-usure et anticorrosif à base de nitrure de chrome. A cause des conditions de sollicitations sévères auxquelles les outils de coupe sont soumis en plus des enjeux environnementaux liés à l’utilisation des fluides de coupe lors de l’usinage du bois, les monocouches qui constituent notre système multicouches doivent présenter des caractéristiques spécifiques. De ce fait, des couches minces de Cr, CrN et CrAlN ont été déposées sur un acier à outils de coupe du bois et sur des substrats de siliciums par pulvérisation magnétron réactive DC. Nous nous sommes intéressés dans un premier temps à optimiser les monocouches. Ensuite, ces revêtements ont été associés pour élaborer des multicouches Cr/CrN/CrAlN qui ont alors été caractérisées. Nous avons étudié les propriétés physico-chimiques, mécaniques, tribologiques et le comportement à la corrosion de différents revêtements multicouches. Les résultats obtenus indiquent que l’application d’un revêtement multicouches pouvait apporter des améliorations considérables à la résistance à l’usure et à la corrosion des outils de coupe du bois. / The aim of this study was to develop and characterize a new generation of wear and corrosion resistant multilayers Cr-N based coatings. Due to the severe conditions that wood cutting tools are subjected in addition to the environmental issue associated with the use of cutting fluids during wood machining, the monolayers that constitute our multilayers system must have specific characteristics. As a result, thin layers of Cr, CrN and CrAlN have been deposited on wood cutting tools steel and silicon substrates by DC reactive magnetron sputtering to be optimized. Then, the optimal monolayerscoatings were combined to develop the Cr/CrN/CrAlN multilayers. that were characterized to determine their physicochemical, mechanical, tribological properties and their corrosion behavior. The results obtained indicated that the application of a multilayer coating can greatly improve the wear and corrosion resistance of a wood cutting tools steel.

O níquel desempenha um papel importante na catálise como uma alternativa ao uso de metais nobres; no entanto, a preparação de nanopartículas de níquel com o tamanho e composição bem controlados não é uma tarefa fácil. O trabalho descrito nessa dissertação compreende a preparação e caracterização de um novo catalisador heterogêneo cotendo nanopartículas de níquel e o estudo da atividade catalítica em reações de hidrogenação em fase gososa e líquida. O catalisador foi preparado por pulverização catódica (magnetron sputtering deposition), que permitiu a deposição de nanopartículas com diâmetro médio de 2,5 ± 0,3 nm sobre um suporte de sílica, sem a utilização de solventes ou estabilizantes. Diferentes tempos de pulverização catódica permitiram a obtenção de catalisadores com diferentes concentrações de metal sobre o suporte. O catalisador preparado foi caracterizado por microscopia eletrônica de transmissão (MET), difração de raios X (DRX), espectroscopia de fotoéletrons excitados por raios X (XPS) e espectroscopia de absorção de raios X (XAS). As análises por técnicas de raios X mostraram que o catalisador oxida parcialmente sua superfície após ser exposto ao ar ambiente. Utilizando XAS, foi possível mostrar que o catalisador como preparado possui 61% de níquel metálico e 39% de níquel óxido. O catalisador exposto ao ar por um ano ainda apresentava 49% de níquel metálico. O desempenho dos catalisadores foi estudado na reação modelo de hidrogenação de cicloexeno, utilizando hidrogênio molecular como agente redutor. Para a hidrogenação em fase líquida, o catalisador não se mostrou ativo nas condições estudadas e não pode ser ativado mesmo após pré-tratamento com hidrogênio molecular. Já na hidrogenação em fase gasosa, o catalisador apresentou atividade catalítica, sendo mais ativo quando submetido a um processo de ativação com fluxo de hidrogênio e aquecimento até 200 ºC. O catalisador perde atividade ao ser utilizado por um longo período ou utilizado em sucessivos ciclos de aquecimento em condições reacionais, mas a atividade pode ser recuperada quando o catalisador é tratado termicamente sob fluxo de hidrogênio. / Nickel plays an important role in catalysis as an affordable alternative for noble metals; however, it is one of the most difficult metal nanoparticles to prepare with well-controlled size and composition. This master thesis comprises the development and characterization of a new heterogeneous catalyst containing nickel nanoparticles and the catalytic studies for hydrogenation reactions in liquid and gas phase. The catalyst was prepared by magnetron sputtering deposition, allowing the deposition of nanoparticles of 2.5 ± 0.3 nm on silica, without using solvents and stabilizers. Different sputtering times allowed the preparation of catalysts with different loading of metal on silica. The catalyst prepared has been characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The analysis by X-ray techniques revealed that the catalyst partially oxidize its surface after being exposed to ambient air. By XAS technique, it was possible to show that the catalyst as prepared has 61% of metallic nickel and 39% of nickel oxide. The as prepared catalyst was exposed to air for a year still contains 49% of metallic nickel. The performance of the catalyst was studied in cyclohexene hydrogenation model reaction, using molecular hydrogen as reducing agent. The catalyst was not active for the liquid phase hydrogenation under the studied conditions, and could not be activated by a pre-treatment with hydrogen. In the gas phase hydrogenation, the catalyst showed catalytic activity being more active when submitted to an activation process with hydrogen flow and heating to 200 ºC. The catalyst loses activity when used for a long time on stream or used in consecutive heating cycles under reaction conditions, but the activity can be regenerated when the catalyst is heat-treated under hydrogen flow.

O níquel desempenha um papel importante na catálise como uma alternativa ao uso de metais nobres; no entanto, a preparação de nanopartículas de níquel com o tamanho e composição bem controlados não é uma tarefa fácil. O trabalho descrito nessa dissertação compreende a preparação e caracterização de um novo catalisador heterogêneo cotendo nanopartículas de níquel e o estudo da atividade catalítica em reações de hidrogenação em fase gososa e líquida. O catalisador foi preparado por pulverização catódica (magnetron sputtering deposition), que permitiu a deposição de nanopartículas com diâmetro médio de 2,5 ± 0,3 nm sobre um suporte de sílica, sem a utilização de solventes ou estabilizantes. Diferentes tempos de pulverização catódica permitiram a obtenção de catalisadores com diferentes concentrações de metal sobre o suporte. O catalisador preparado foi caracterizado por microscopia eletrônica de transmissão (MET), difração de raios X (DRX), espectroscopia de fotoéletrons excitados por raios X (XPS) e espectroscopia de absorção de raios X (XAS). As análises por técnicas de raios X mostraram que o catalisador oxida parcialmente sua superfície após ser exposto ao ar ambiente. Utilizando XAS, foi possível mostrar que o catalisador como preparado possui 61% de níquel metálico e 39% de níquel óxido. O catalisador exposto ao ar por um ano ainda apresentava 49% de níquel metálico. O desempenho dos catalisadores foi estudado na reação modelo de hidrogenação de cicloexeno, utilizando hidrogênio molecular como agente redutor. Para a hidrogenação em fase líquida, o catalisador não se mostrou ativo nas condições estudadas e não pode ser ativado mesmo após pré-tratamento com hidrogênio molecular. Já na hidrogenação em fase gasosa, o catalisador apresentou atividade catalítica, sendo mais ativo quando submetido a um processo de ativação com fluxo de hidrogênio e aquecimento até 200 ºC. O catalisador perde atividade ao ser utilizado por um longo período ou utilizado em sucessivos ciclos de aquecimento em condições reacionais, mas a atividade pode ser recuperada quando o catalisador é tratado termicamente sob fluxo de hidrogênio. / Nickel plays an important role in catalysis as an affordable alternative for noble metals; however, it is one of the most difficult metal nanoparticles to prepare with well-controlled size and composition. This master thesis comprises the development and characterization of a new heterogeneous catalyst containing nickel nanoparticles and the catalytic studies for hydrogenation reactions in liquid and gas phase. The catalyst was prepared by magnetron sputtering deposition, allowing the deposition of nanoparticles of 2.5 ± 0.3 nm on silica, without using solvents and stabilizers. Different sputtering times allowed the preparation of catalysts with different loading of metal on silica. The catalyst prepared has been characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The analysis by X-ray techniques revealed that the catalyst partially oxidize its surface after being exposed to ambient air. By XAS technique, it was possible to show that the catalyst as prepared has 61% of metallic nickel and 39% of nickel oxide. The as prepared catalyst was exposed to air for a year still contains 49% of metallic nickel. The performance of the catalyst was studied in cyclohexene hydrogenation model reaction, using molecular hydrogen as reducing agent. The catalyst was not active for the liquid phase hydrogenation under the studied conditions, and could not be activated by a pre-treatment with hydrogen. In the gas phase hydrogenation, the catalyst showed catalytic activity being more active when submitted to an activation process with hydrogen flow and heating to 200 ºC. The catalyst loses activity when used for a long time on stream or used in consecutive heating cycles under reaction conditions, but the activity can be regenerated when the catalyst is heat-treated under hydrogen flow.

Les TCOs (Transparent Conductive Oxide) trouvent des applications dans de nombreux domaines s'étendant del'électrochromie au photovoltaique en passant par l'opto-électronique. Parmi les matériaux historiques, les TCOs detype n font l'objet d'une littérature abondante tandis que les TCO de type p sont quant à eux étudiés de façon plusconfidentielle mais commencent à susciter un engouement, notamment dans l'objectif de jonctions p-ntransparentes.Sur la base de la théorie de la méthode de modulation chimique de bande de valence, le composé CuCrO2 destructure délafossite est considéré comme un candidat intéressant de TCO de type p. L'objectif de ces travaux estd'élaborer des films minces à base de CuCrO2 avec une transmittance optique acceptable et une conductivitéélectrique de type p élevée afin de envisager la possibilité de fabrication des jonctions p-n transparents pourdiverses applications.Dans ce travail, les films CuCrO2 ont été déposés par co pulvérisation cathodique magnétron en condition réactiveà partir de cibles métalliques. Une substitution partielle de Cr par Mg a ensuite été effectuée et l'influence del'épaisseur du film CuCrO2 :Mg sur ses propriétés optoélectroniques a été étudiée. Enfin, des revêtementsd'architecture sandwich CuCrO2 :Mg/Ag/CuCrO2 :Mg ont été élaborés en faisant varier le temps de dépôt de lacouche intermédiaire d'argent afin d'améliorer les performances optoélectroniques des films. / Transparent conductive oxides (TCOs) can be widely used in various domains from electrochromics to photovoltaicsowing to their unique optoelectronic properties. During the history of the development of TCOs, most attention hasbeen focused on n-type TCOs, while p-type TCOs have made slow progress. Recently, the studies on p-type TCOsraised many interest especially due to their potential application in the fabrication of transparent p-n junctions.Based on the theory of chemical method of valance band, CuCrO2 compound with delafossite structure isconsidered as an interesting candidate for p-type TCOs. The objective of this work is to synthesize CuCrO2-basedthin films with acceptable optical transmittance and high p-type electrical conductivity in order to explore thepossibility of fabrication of transparent p-n junctions for various applications.In this work, CuCrO2 films were deposited by reactive sputtering from metallic targets. Then, partial Cr substitutionby Mg was performed into CuCrO2 films and the influence of the films thickness on its optoelectronic properties wasstudied. Finally, sandwich architectural coatings of CuCrO2 :Mg/Ag/CuCrO2 :Mg were designed in order to improvethe films optoelectronic performances.

Les zirconates titanates de plomb (PZT) suscitent un intérêt considérable pour plusieurs applications industrielles, au regard de leurs excellentes propriétés piézoélectriques et électromécaniques. Le contexte actuel de l’innovation technologique est la miniaturisation et l’allègement des produits ; c’est pour cette raison que de nombreuses études sont menées depuis une vingtaine d’années sur les techniques et les procédés de synthèse de ces matériaux piézoélectriques sous forme de couches minces tout en garantissant une fiabilité accrue. Dans ce contexte, l’étude menée dans le cadre de cette thèse, a visé l’optimisation du procédé d’élaboration de films minces piézoélectriques de PZT par pulvérisation cathodique magnétron en mode DC et en mode Rf, en vue d’obtenir des capteurs d’efforts piézoélectriques. La synthèse in situ et la cristallisation ex-situ des films élaborés, par recuit classique (CFA) ou recuit rapide (RTA) confirme une structure pérovskite du PZT, complétées par une série de caractérisations morphologiques et structurales. Les domaines ferroélectriques à l’origine des propriétés piézoélectriques sont correctement visualisés par PFM et le calcul du coefficient piézoélectrique d33 des couches synthétisées sur des substrats métalliques, est réalisé par interféromètre laser. En parallèle, une approche expérimentale est menée sur l’évolution des performances piézoélectriques des films de PZT d’une part en fonction du mode d’élaboration et d’autre part en fonction de la texturation des couches, assurée par des traitements thermiques de cristallisation. / Recently, PZTs thin films have been spotlighted for various applications owing to their excellent piezoelectric and electromechanical properties. Most of the existing coating methods have been explored for the deposition of PZT. In this work, amorphous Pb(ZrxTi1-x)O3 (PZT) thin films were prepared by pulsed DC and RF magnetron sputtering in order to device a piezoelectric force sensors. The structure of a perovskite phase of PZT thin films was successfully characterized and morphological characterizations were investigated. Ferroelectrics properties of PZT thin films were determined using Piezoresponse Force Atomic technique (PFM) while the functional response of the films was characterized by measurements of piezoelectric d33 coefficients. Additionally, the coating processes and the crystallization behavior at different temperatures, of amorphous PZT thin films during either conventional furnace annealing (CFA) or rapid thermal annealing (RTA) were studied to understand the evolution of piezoelectric properties of films.

<p>High power impulse magnetron sputtering (HiPIMS) is a novel pulsed power technique. In HiPIMS, high power pulses are applied to the target for short duration with a low duty factor. It provides a high degree of ionization of the sputtered material (in some cases up to 90%) and a high plasma density (10¹⁹ m^-3) which results in densification of the grown films. Recently a large side-transport of the sputtered material has been discovered, meaning that the sputtered material is transported radially outwards, parallel to the cathode surface. In this research, we use this effect and study the side-ways deposition of thin films. We designed a new magnetron sputtering system, consisting of two opposing magnetrons with similar polarity. Ti films were grown on Si using the side-ways transport of the sputtered material. Scanning electron microscope was employed to investigate the microstructure of the grown films. Optical emission spectroscopy (OES) measurements were made for investigating the ionized fraction of the sputtered material while Langmuir probe measurements were made for evaluating the plasma parameters such as electron density. The conclusion is that the system works well for side-ways deposition and it can be useful for coating the interior of cylindrically shaped objects. It is a promising technique that should be used in industry.</p>