<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>

Barium Strontium Titanate (BST) based ferroelectric thin film devices have been popular over the last decade due to their versatile applications in tunable microwave devices such as delay lines, resonators, phase shifters, and varactors. BST thin films are promising candidates due to their high dielectric constant, tunability and low dielectric loss. Dielectric-tunable properties of BST films deposited by different deposition techniques have been reported which study the effects of factors, such as oxygen vacancies, film thickness, grain size, Ba/Sr ratio, etc. Researchers have also studied doping concentrations, high temperature annealing and multilayer structures to attain higher tunability and lower loss. The aim of this investigation was to study material properties of Barium Strontium Titanate from a comprehensive point of view to establish relations between various growth techniques and the film physical and electrical properties. The primary goal of this investigation was to synthesize and characterize RF magnetron sputtered Barium Strontium Titanate (Ba1-xSrxTiO3), thin film structures and compare their properties with BST thin films deposited by sol-gel method with the aim of determining relationships between the oxide deposition parameters, the film structure, and the electric field dependence. In order to achieve higher thickness and ease of fabrication, and faster turn around time, a `stacked' deposition process was adopted, wherein a thin film (around 200nm) of BST was first deposited by RF magnetron sputtering process followed by a sol-gel deposition process to achieve higher thickness. The investigation intends to bridge the knowledge gap associated with the dependence of thickness variation with respect to the tunability of the films. The film structures obtained using the three different deposition methods were also compared with respect to their analytical and electrical properties. The interfacial effect on these `stacked' films that enhance the properties, before and after annealing these structures was also studied. There has been significant attention given to Graphene-based supercapacitors in the last few years. Even though, supercapacitors are known to have excellent energy storage capability, they suffer from limitations pertaining to both cost and performance. Carbon (CNTs), graphene (G) and carbon-based nanocomposites, conducting polymers (polyaniline (PANI), polypyrrole (PPy), etc.) have been the fore-runners for the manufacture of supercapacitor electrodes. In an attempt to better understand the leakage behavior of Graphene Polyaniline (GPANI) electrodes, BST and BST thin films were incorporated as constituents in the process of making supercapacitor electrodes resulting in improved leakage behavior of the electrochemical cells. A detailed physical, chemical and electrochemical study of these electrochemical cells was performed. The BST thin films deposited were structurally characterized using Veeco Dektek thickness profilometer, X-ray diffraction (XRD), Scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques. The interfacial structural characterization was carried out using high-resolution transmission electron microscopy (HRTEM). This investigation, also presents noncontact electrical characterization of BST films using Corona Kelvin metrology (C-KM). The `stacked' BST thin films and devices, which were electrically tested using Corona Kelvin metrology, showed marked improvement in their leakage characteristics over both, the sputtered and the sol-gel deposited counterparts. The `stacked' BST thin film samples were able to withstand voltages up to 30V positive and negative whereas, the sol-gel and sputtered samples could hold only up to a few volts without charge leaking to reduce the overall potential. High frequency, 1GHz, studies carried out on BST thin film interdigitated capacitors yielded tunability near 43%. Leakage barrier studies demonstrated improvement in the charging discharging response of the GPANI electrochemical electrodes by 40% due to the addition of BST layer.

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%. <b>Key words:</b>ferroelectrics, sodium potassium niobates,thin films, rf-magnetron sputtering, waveguiding, refractiveindex, prism coupling, dielectric tunability / NR 20140805

L'objectif de cette thèse était d'étudier les propriétés thermoélectriques de couches minces d'oxyde de type delafossite déposées par pulvérisation cathodique magnétron. Pour cela, les oxydes CuCrO2:3%Mg, CuFeO2:3%Mg et CuCr0,84Fe0,16O2:3%Mg ont été déposés avec différentes épaisseurs sur des substrats de silice amorphe puis traités sous vide à différentes températures afin d'obtenir la structure delafossite. La température de traitement thermique optimale permettant d'obtenir les meilleures propriétés thermoélectriques est de 550°C pour CuCrO2:Mg et CuCr0,84Fe0,16O2:Mg et de 700°C pour CuFeO2:Mg. L'épaisseur optimale des couches minces est de 100 nm pour la delafossite au chrome et de 300 nm pour celle au fer. La conductivité électrique des couches augmente avec la température tout en conservant un coefficient Seebeck positif et constant pour les trois compositions données impliquant un mécanisme par saut de polarons. Le facteur de puissance des couches minces CuCrO2:Mg, CuFeO2:Mg et CuCr0,84Fe0,16O2:Mg dont l'épaisseur et la température de recuit ont été optimisées atteint respectivement 59 µW.m-1K-2, 84 µW.m-1K-2 et 36 µW.m-1K-2 à 200°C. Les études microstructurales et structurales ont permis de comprendre la variation du facteur de puissance avec la température de recuit et l'épaisseur. Elles ont notamment montré que la décroissance de la conductivité électrique des films traités à haute température est due à des phénomènes concomitants de fissuration de la couche et de ségrégation du magnésium. Une étude thermique utilisant la modélisation avec la méthode des éléments finis a permis de démontrer que dans le cas des couches minces, la conductivité thermique du substrat peut se substituer à celle du film dans le calcul de facteur de mérite. La validité du facteur de mérite modifié ((ZT)* = S2σ/ksubstrat) a été énoncée en fonction de l'épaisseur, l'émissivité et la conductivité thermique de la couche mince. L'utilisation de la méthode 3ω a permis de déterminer une valeur de conductivité thermique de 4,82 W.m-1k-1 à 25°C pour le film mince CuFeO2:Mg, qui se situe dans le domaine de validité établi pour l'utilisation de (ZT)*.[...] / The aim of this thesis was to study the thermoelectric properties of delafossite type oxides thin-films deposited by RF-magnetron sputtering. Several thicknesses of CuCrO2:3%Mg, CuFeO2:3%Mg and CuCr0,84Fe0,16O2:3%Mg oxides were deposited on fused silica then annealed under vacuum at different temperatures in order to obtain delafossite structure. The optimal annealing temperature which leads to an acceptable thermoelectric properties is 550°C for CuCrO2:Mg and CuCr0,84Fe0,16O2:Mg thin films and 700°C for CuFeO2:Mg thin film. The optimal thickness is 100 nm for the delafossite with chrome and 300 nm for delafossite with iron. The electrical conductivity of the studied thin films increases with the temperature, while maintaining a positive and constant Seebeck coefficient for the three given compositions that implies a hopping mechanism. The power factor of CuCrO2:Mg, CuFeO2:Mg and CuCr0,84Fe0,16O2:Mg thin films for which the annealing temperature and the thickness were optimized, reached 59 µW.m-1K-2, 84 µW.m-1K-2 and 36 µW.m-1K-2 respectively at 200°C. The microstructural and structural analysis allowed to understand the variation of the power factor with the annealing temperatures and the thicknesses. In particular, they showed that the decrease in the electrical conductivity of the thin films annealed at high temperature is due to concomitant phenomena of film cracking and magnesium segregation. A thermal analysis using modeling with the finite element method has demonstrated that in the case of thin films, the thermal conductivity of the substrate can be substituted for the thermal conductivity of the film in the calculation of figure of merit. The validity of the modified figure of merit ((ZT)* = S2σ/ksubstrate) was given as a function of the film thickness, emissivity and thermal conductivity. The thermal conductivity of CuFeO2:Mg was measured using the 3ω method and it was 4.82 W.m-1k-1 at 25°C which is within the range of validity established for the use of (ZT)*[...]

Microwave materials have been widely used in a variety of applications ranging from communication devices to military satellite services, and the study of materials properties at microwave frequencies and the development of functional microwave materials have always been among the most active areas in solid-state physics, materials science, electrical and electronic engineering. In recent years, the increasing requirements for the development of high speed, high frequency circuits and systems require complete understanding of the properties of materials function at microwave frequencies. Ferroelectric materials usually have high dielectric constant, and their dielectric properties are temperature and electric field dependent. The change in permittivity as a function of electric field is the key to a wide range of applications. Ferroelectric materials can be used to fabricate capacitors for electronic industry because of their high dielectric constant, and this is important in the trend toward miniaturization and high functionality of electronic products. The simple tunable passive component based on ferroelectric films is a varactor which can be made as a planar structure and used for electrically tunable microwave integrated circuits. It is an important task to sinter highly tunable and low loss ferroelectrics, fabricate and test the properties of microwave ferroelectric components. This thesis shows experimental results on growth, crystalline and microwave properties of Na0.5K0.5NbO3 (NKN), AgTa0.5Nb0.5O3 (ATN), Ba0.5Sr0.5TiO3 (BST) as well as AgTaO3 (ATO), and AgNbO3 (ANO) thin films. The films were grown by Pulsed Laser Deposition (PLD) and rf-magnetron sputtering techniques from stoichiometric high density ceramic NKN, ATN, ATO, ANO and BST targets onto LaAlO3 (LAO), Al2O3 (r-cut sapphire), Nd:YAlO3 single crystals and amorphous glass substrates. Advanced X-ray diffraction examinations showed NKN, ATN, BST films on LAO substrates grow epitaxially, whereas films on r-cut sapphire were found to be preferentially (00l) oriented. Coplanar waveguide 2 µm finger gap interdigital capacitor (CPWIDC) structures were fabricated by photolithography process and metal lift-off technique. On-wafer tests up to 40 GHz were performed to characterize microwave properties of the ferromagnetic film CPWIDC devices. The measurement setup is composed of network analyzer, probe station, and microwave G-S-G probes. External electric field was applied to planar capacitors to measure tunability. Original de-embedding technique has been developed to calculate capacitance, loss tan δ, and tunability of varactors from the measured S-parameters. NKN film interdigital capacitors on Nd:YAlO3 showed superior performance compared to ATN in the microwave range from 1 to 40 GHz. Within this range, the voltage tunability (40V, 200 kV/cm) was about 29%, loss tangent ~ 0.13, K-factor = tunability/tan δ from 152% @ 10GHz to 46% @ 40GHz. The ATN/sapphire CPWIDCs showed the lowest dispersion ~ 4.3% in whole frequency range from 1 to 40 GHz, voltage tunability 4.7% @ 20GHz and 200 kV/cm, lowest loss tangent ~ 0.068 @ 20GHz, K-factor = tunability/tan δ ranged from 124% @ 10GHz to 35% @ 40GHz. BST film CPWIDCs on sapphire showed frequency about 17%, the highest voltage tunability ~ 22.2%, loss tangent ~ 0.137 @ 20GHz, and K-factor = 281% @ 10GHz to 95% @ 40GHz. / QC 20100906

Ferroelectric oxides are a group of advanced electronic materials with a wide variety of properties useful in applications such as memory devices, resonators and filters, infrared sensors, microelectromechanical systems, and optical waveguides and modulators. Among the oxide perovskite-structured ferroelectric thin film materials, sodium potassium niobate or Na0.5K0.5NbO3 (NKN) has recently emerged as one of the most promising materials in radio frequency (rf) and microwave applications due to high dielectric tenability and low dielectric loss. This thesis presents results on growth and structural, optical, and electrical characterization of NKN thin films. The films were deposited by rf-magnetron sputtering of a stoichiometric, high density, ceramic Na0.5K0.5NbO3 target onto single crystal LaAlO3 (LAO), Al2O3 (sapphire), SrTiO3, and Nd:YAlO3, and polycrystalline Pt80Ir20 substrates. By x-ray diffractometry, NKN films on c-axis oriented LaAlO3, SrTiO3 and Nd:YAlO3 substrates were found to grow epitaxially, whereas films on r-cut sapphire and polycrystalline Pt80Ir20 substrates were found to be preferentially (00l) oriented. The surface morphology was explored using atomic force microscopy. Optical and waveguiding properties of the Na0.5K0.5NbO3/substrate heterostructures were characterized using prism-coupling technique. Sharp and distinguishable transverse magnetic and electric propagation modes were observed for NKN thicknesses up to 2.0 μm. The extraordinary and ordinary refractive indices were calculated together with the birefringence of the NKN material. The electro-optic effect in transverse geometry was measured in transmission, where the effective linear electro-optic response was determined to reff = 28 pm/V for NKN/Al2O3 with an applied dc field up to 18 kV/cm. The ferroelectric state in NKN films on Pt80Ir20 at room temperature was indicated by a polarization loop with saturated polarization as high as 33.4 μC/cm2 at 700 kV/cm, remnant polarization of 10 μC/cm2, and coercive field of 90 kV/cm. Current-voltage characteristics of vertical Au/NKN/PtIr capacitive cells and planar Au/NKN/LAO interdigital capacitors (IDCs) showed very good insulating properties, with the leakage current density for an NKN IDC on the order of 30 nA/cm2 at 400 kV/cm. Rf dielectric spectroscopy demonstrated low loss, low frequency dispersion, and high voltage tunability. At 1 MHz, NKN/LAO showed a dissipation factor tan δ = 0.010 and a tunability of 16.5 % at 200 kV/cm. For the same structure the frequency dispersion was Δεr = 8.5 % between 1 kHz and 1 MHz. / QC 20100928

Co-doped ZnO (ZnO:Co) thin film with room temperature ferromagnetism and spin polarized carriers is one of the advance materials and highly applicable in future development in spintronics. When ZnO:Co films deposited by a £_ growth method in a ion sputtering system, low solubility of Co (3.75%) limits further applications such that a single-guns sputtering thin film growth technique is employed in this study to outreach this limitation. A ZnO:Co bulk with 5 at% of Co was formed by a solid reaction method and used as a target. ZnO:Co films were grown in a single-gun RF sputtering system. However, all films grown at room temperature were insulator which might because sufficient oxygen content in the target and the negative charge of oxygen ion moving toward substrate making the films of full oxygen content. In this study, the post annealing in vacuum environment and the deposition of films in hydrogenation environment are conducted to try to produce various level of oxygen vacancies in the films for understanding the interplay between the oxygen vacancies and the electric transport and magnetic coupling. The present experiment contains two parts: (1) grow films with various thicknesses by controlling deposition time and then applying post annealing process, and (2) grow the films in oxygen reduced environment by introducing hydrogen during growth and taking out partial oxygen content in the plasma and the films. In the first part, the grain sizes of the films are near constant while the crystal quality is improved with the thickness of films. The worse crystal quality of grains, the better the electric transport and the stronger the magnetic coupling after post annealing processes. This indicates that the electric transport and magnetic coupling could be improved when the thin films was formed by crystals with certain disordering and contained a certain level of oxygen vacancies. In the second part, the introduced hydrogen may combine with the oxygen sputtered out from the target before deposition on substrates. It means that the films are grown in oxygen deficient conditions and result in various degrees of oxygen vacancies. Zn clusters precipitate in films when the concentration of hydrogen is over 20%, and at the meantime, they increase the conductivity and suppress the magnetic coupling in the films. These discoveries provide new perspective in understand the electric transport and ferromagnetism mechanics in DMS materials.

This work deals with deposition of yttrium oxide layers on silicon substrate (P – type) by using magnetron and reactive magnetron sputtering. Experiments which were made are further described. After that, work is focused on evaluation of deposited layers by using FTIR measurement technique and spectrophotometry. At the end of the work results of experiments are discussed also with the future progress.

Smooth fluorocarbon plasma polymer films have been for a long time considered for fabrication of hydrophobic and slippery coatings. Interest in fluorocarbon materials was also supported by their excellent self-lubricant, dielectric properties and chemical inertness. This thesis is focused on development of new methods for fabrication of fluorocarbon plasma polymes, which could combine the chemical composition and the physical structure necessary for reaching superhydrophobic character of coatings. Poly(tetrafluoroethylene) was the subject material. RF magnetron sputtering using gas aggregation cluster source was the method adapted to fabricate fluorocarbon nanostructured films with chemical composition close to conventional bulk PTFE, but with high degree of cross- linking and branched structure. A model of growth of such plasma polymer nanostructures was discussed.

Le marché du stockage de l'énergie est en perpétuelle expansion, tant pour les applications nomades que fixes. Afin de répondre aux exigences requises pour les diverses applications (appareils électroniques, véhicules hybrides et électriques, stockage des énergies renouvelables…), des batteries toujours plus performantes, compactes et légères doivent être développées. Pour cela, les batteries utilisant du lithium métallique en tant qu'anode sont les plus attractives en termes de densités d'énergies. Néanmoins, l'utilisation d'électrolytes liquides conventionnels, généralement des solvants organiques inflammables, dans de tels dispositifs soulève des problématiques de sécurité. Les travaux de recherche présentés dans ce manuscrit concernent l'étude de matériaux vitreux pouvant être utilisés en tant qu'électrolyte solide afin de permettre le développement de batteries tout-solide sûres et performantes. Des verres de sulfures au lithium, attractifs pour leurs propriétés de conduction ionique, sont étudiés et caractérisés. Les propriétés de conduction ionique dans les verres étant toujours mal comprises et sujettes à controverses, l'analyse structurale des verres présente ici un réel intérêt pour une meilleure compréhension des corrélations entre structure et propriétés. Un effort de recherche a donc été porté sur l'étude de l'ordre local dans les verres préparés via différentes techniques d'analyse structurale complémentaires. Enfin, les matériaux vitreux, sont de manière générale relativement faciles à mettre en forme. Les verres étudiés dans ce manuscrit peuvent alors également être utilisés en tant qu'électrolytes sous forme de couches minces dans les micro-batteries. Des premiers essais de dépôts par pulvérisation cathodique RF magnétron de couches minces conductrices ont donc été effectués et constituent la première brique à la fabrication de micro-batteries. / The energy storage market is in constant growth for both portable and stationary applications. To satisfy the requirements of various applications (electronic devices, hybrid-electric vehicles, renewable energy storage…), always more efficient, more compact and lightweight batteries have to be developed. Then, thanks to their high energy densities, batteries using Li metal anodes are the most promising to complete this challenge. However, the use of conventional liquid electrolytes raises safety issues, mainly related to the flammability of the organic liquid. In this thesis, glassy materials, exhibiting great interest towards developing solid electrolytes are considered and might enable the development of safe and efficient all-solid-state batteries. Here, Li-sulfide glasses, attractive for their ionic conduction properties, have been studied and characterized. The ionic conduction properties of glasses are still misunderstood and controversial, the structural investigation of glasses is of great interest in order to get a better understanding of structure-properties relationship. Then, the short and intermediate range order of prepared glasses have been investigated by the mean of various complementary structural analysis techniques. Finally, glassy materials are usually quite easy to shape. Thus, studied glasses in this thesis can also be used as thin-film electrolytes in microbatteries. First tests of sputtering of conducting thin-films have been performed by RF magnetron sputtering and constitute a first step in order to design microbatteries.