Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Granular magnetic systems can be composed by magnetic particles or clusters with size of some nanometers. These magnetic nanoparticles present different magnetic order phases, as superparamagnetic, and they can be embedded in both, metallic or insulating matrix. These systems present several phenomena such as the giant magnetoresistance (GMR), tunnel magnetoresistance (TMR) and Coulomb blockade. That phenomena use to disappear when a small termal fluctuation is high enough to reverse the magnetization of the clusters leading the lost the magnetic information in a very short time range. When it occurs, the nano-particles are in superparamagnetic phase. In order to maintain the magnetic information at high values of temperature, or even to suppress the superparamagnetic limit, many works have tried to use an antiferromagnetic matrix, to induce the increase of the energy barrier among the two directions of magnetization easy by the exchange coupling in the grain(FM)/matrix(AFM) interfaces, with the purpose of stabilizing the nano-particles magnetization. In this work, we have produced Co granular samples inside an Al2O3/CoO insulating/antifferomagnetic matrix through a sequential deposition by magnetron sputtering. We aim to explore the couplingmechanisms among the ferromagnetic nanoparticles and the antiferromagnetic matrix. It has been performed measurements of Impedance Spectroscopy (IS), X-ray Difraction (XRD), and magnetization at function temperature analysed by zero-field cooling/field cooling curves (ZFC-FC) at some samples in order to obtain information about the magnetic and structural properties. The measurements of IS and XRD corroborate the formation of Co clusters and the magnetization versus temperature curves to some samples do not indicate evidence of the exchange coupling among the Co clusters and the CoO antiferromagnetic matrix. / Sistemas granulares magnéticos podem ser formados por grãos ou aglomerados magnéticos cujo tamanho é de alguns nanômetros. Estes nano-grãos magnéticos apresentam diferentes fases de ordenamento magnético, como o superparamagnetismo, e podem estar envolvidos tanto por matrizes metálicas como matrizes isolantes. Estes sistemas possuem uma riqueza de fenômenos, como a magnetorresitência gigante (GMR), magnetorresistência túnel (TMR), bloqueio de coulomb entre outros. Estes fenômenos muitas vezes desaparecem quando uma flutuação térmica for suficiente para inverter a magnetização dos grãos, levando-os a perder informação magnética num intervalo de tempo muito curto. Quando isto ocorre dizemos que os nano-grãos estão na fase superparamagnética. Para reter a informação magnética a temperatura ambiente, ou até mesmo suprimir o superparamagnetismo, tem-se tentado o uso de uma matriz antiferromagnética (AFM) onde os nano-grãos ficam imersos, e o acoplamento de troca na interface grão (FM)/matriz (AFM) pode induzir um aumento na barreira de energia entre as duas direções de fácil magnetização e com isso estabilizar a magnetização dos nano-grãos. Neste trabalho foram produzidas amostras granulares de Co imersos em matriz isolante/antiferromagnética de Al2O3/CoO pela deposição alternada do metal e dos isolantes por magnetron sputtering , com a finalidade de explorar os mecanismos de acoplamento entre os nano-grãos ferromagnéticos e a matriz antiferromagnética. Foram realizadas medidas de Espectroscopia de Impedância (IS), Difração de raios-X (XRD), e magnetização em função da temperatura pelas técnicas ZFC-FC em algumas amostras, afim de se obter respostas quanto as propriedades estruturais e magnéticas. As medidas de IS e XRD, indicam a formação de nano-grãos Co e as medidas de magnetização em função da temperatura para algumas amostras, não mostraram com evidência o acoplamento de troca ( Exchange Bias ) entre os grãos de Co e a matriz antiferromagnética de CoO.

The subject of the master thesis is the extension of the measurement of plasma para- meters by the Langmuir probe in a system with a planar magnetron and a hollow cathode operating in pulse mode. The main tasks are to modify the measuring circuit to increase the maximum probe current and to put the USB oscilloscope into operation for data collection with higher resolution and higher sampling rate. Furthermore, the function of the entire device will be verified using test circuits and also by measuring the probe characteristics in discharges in a system with a magnetron and a hollow cathode in both continuous and pulse mode. 1

<p>The technique of magnetron sputtering is considered for the deposition of silicon rich films. Attention was paid to the possibility to produce light emitting silicon rich films by three different methods, such as reactive magnetron sputtering, co-sputtering from silicon/silicon dioxide targets and a stacked film approach. It was found that photoluminescence of the films deposited in presence of hydrogen was much grater then that for other samples.</p> <p>A model of reactive sputter deposition was also developed and tested in this work. Results achieved in numerical simulation are compared with experimental data and show a good correlation.</p> <p>An experimental unit for magnetron sputtering was designed and built based on a sphere-shaped vacuum chamber equipped with a commercially available magnetron sputter gun, RF generator as power supply unit, vacuum controllers, mass flow controllers, in-situ thickness monitor, temperature controller and other supplemental equipment.</p> <p>Characterization of deposited film was made usmg Profile Measurement, ellipsometry, Rutherford Back Scattering measurements, X-Ray Diffraction measurements and photoluminescence measurements.</p> <p>The achieved results show the principal possibility of getting microcrystalline silicon films and light emitting silicon nanocrystals embedded into silicon dioxide matrix by the sputter deposition technique.</p> / Master of Science (MS)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Ta-Al-N thin films were prepared using reactive magnetron sputtering, in order to verify the influence of the aluminum content on the crystalline structure, hardness and oxidation resistance. The samples were characterized by Grazing Incidence X-ray Diffraction (GIXRD), Energy Dispersive Spectroscopy (EDS), Rutherford Backscattering Spectrometry (RBS), nanohardness analysis and oxidation tests at 500°C, 600°C and 700°C. First, it was necessary to define deposition parameters of stoichiometric TaN with face centered cubic structure. From this, TaAlN thin films were prepared and present at concentration of 2, 5, 7, 14, 24 and 41 at.%. The crystal phase for the TaAlN films was only present with addition up to 5 at.%, increasing the Al concentration the coatings will tend to be amorphous. From the SEM analysis was possible to observe the surface of the film after oxidation, all thin films showed irregularities, however the amount of such failures was lower in samples with low aluminum content. Moreover, the addition of aluminum does not result in significant gains for oxidation resistance. The highest hardness value obtained was 29 GPa for the sample containing 14 at.%. / Filmes finos de Ta-Al-N foram depositados por magnetron sputtering reativo, com o intuito de verificar a influência da variação do teor de alumínio na estrutura cristalina, na dureza e na resistência à oxidação desse revestimento. As amostras foram caracterizadas por Difração de Raios X em ângulo rasante (GAXRD), Microscopia Eletrônica de Varredura (MEV), Espectroscopia de Energia Dispersiva (EDS), Espectroscopia por Retroespalhamento Rutherford (RBS), análises de nanodureza e testes de oxidação a temperaturas de 500°C, 600°C e 700°C. Primeiro foi necessário definir os parâmetros de deposição de filmes finos de TaN estequiométrico e com estrutura cubica de face centrada. A partir disso, filmes finos de TaAlN foram depositados e apresentaram concentração de 2, 5, 7, 14, 24 e 41 at.% de Al. A fase cristalina obtida para os filmes de TaAlN se apresentou constate com a adição de até 5 at.% de Al, com o aumento da concentração de Al o filme passa a ter uma tendência a ser amorfo. A partir das análises de MEV foi possível observar a superfície dos filmes após a oxidação, todos os filmes apresentaram irregularidades na superfície, entretanto a quantidade dessas falhas foi menor nas amostras com menores concentrações de alumínio. Além disso, a adição de alumínio não trouxe ganhos significativos para a resistência à oxidação desse revestimento. O maior valor de dureza obtido foi de 29 GPa para as amostras contendo 14 at.%.

The thesis has dealt with transparent conducting oxide (TCO) materials, with a focus on Al:ZnO and with studies on Sn:In2O3 and ZnO. TCOs are a material group that is used for its properties of being conductive and at the same time transparent. In solar cells, a top layer of TCO is often used to allow light to transmit into the cell and then conduct the resulting current.   A set of growth parameters was chosen and optimized through a literature study and experiments. The depositied thin films were characterized by optical and electrical characterization methods. Rf-magnetron-sputtering was used as the deposition method, where the influence of O2, argon and substrate temperature were the parameters to be studied. As a part of the characterization a model for spectroscopic ellipsometry on Al:ZnO was made, enabling faster measurement of transport properties. The main parameter affecting the TCO properties was found to be oxygen flow and the optimum flow value for each material has been determined. Substrate heating did not show any significant improvement on the resistivity of Al:ZnO with a minimum value of ~5.0*10-4 Ωcm while no heating resulted in a value of ~6.0*10-4  Ωcm. These values are comparable to the state-of-the-art from the literature.   As a demonstration of application, the developed AZO and ZnO were applied to CIGS solar cells and these were compared to a reference. The newly developed AZO and ZnO was comparable to the reference but a lower mean fill factor indicates that improvements can be made.

This dissertation discusses a number of theoretical models of coupled bosonic modes, all closely related to the Bose-Hubbard dimer. In studying these models, we will repeatedly return to two unifying themes: the classical structure underlying quantum dynamics and the impact of weakly coupling a system to an environment. Or, more succinctly, semiclassical methods and open quantum systems. Our primary motivation for studying models such as the Bose-Hubbard is their relevance to ongoing ultracold atom experiments. We review these experiments, derive the Bose-Hubbard model in their context and briefly discuss its limitations in the first half of Chapter 1. In its second half, we review the theory of open quantum systems and the master equation description of the dissipative Bose-Hubbard model. This opening chapter constitutes a survey of existing results, rather than original work. In Chapter 2, we turn to the mean-field limit of the Bose-Hubbard model. After reviewing the striking localization phenomena predicted by the mean-field (and confirmed by experiment), we identify the first corrections to this picture for the dimer. The most interesting of these is the dynamical tunneling between the self-trapping points of the mean-field. We derive an accurate analytical expression for the tunneling rate using semiclassical techniques. We continue studying the dynamics near the self-trapping fixed points in Chapter 3, focusing on corrections to the mean-field that arise at larger nonlinearities and on shorter time scales than dynamical tunneling. We study the impact of dissipation on coherence and entanglement near the fixed points, and explain it in terms of the structure of the classical phase space. The last chapter of the dissertation is also devoted to a dissipative bosonic dimer model, but one arising in a very different physical context. Abandoning optical lattices, we consider the problem of formulating a quantum model of operation of the cylindrical anode magnetron, a vacuum tube crossed-field microwave amplifier. We derive an effective dissipative dimer model and study its relationship to the classical description. Our dimer model is a first step towards the analysis of solid-state analogs of such devices.

Doctor of Philosophy / First part of the thesis is focused on experimental preparation of new hard quaternary amorphous materials Si-B-C-N with high thermal stability. Materials were prepared in the form of thin films using reactive magnetron sputtering. The technique used proved to be suitable for reproducible synthesis of these materials. The Si-B-C-N films were generally found to be amorphous with low compressive stress and good adhesion to silicon or glass substrates. The process and film characteristics were controlled by varying the sputter target composition, the Ar fraction in the N2–Ar gas mixture, the negative rf-induced substrate bias, and the substrate temperature. Main conclusions describe the relationships between process parameters, discharge and deposition characteristics and film properties (elemental composition, chemical bonding structure, material hardness, compressive stress or electrical conductivity of materials prepared). Second part of the thesis is focused on ab-initio simulations of structures of experimentally prepared Si-B-C-N materials. In the performed liquid-quench simulations, the Kohn-Sham equations for the valence electrons are expanded in a basis of plane wave functions, while core electrons were represented using Goedecker-type pseudopotentials. We simplified the ion bombardment process by assuming that the primary impact creates a localized molten region of high temperature and sufficiently short cooling time, commonly referred to as a thermal spike. Main conclusions deal with N2 formation in studied materials, effect of implanted Ar on structure and properties of prepared materials, ability of Si to relieve that part of compressive stress which is caused by implanted Ar, and ability of B to improve thermal stability of Si-B-C-N materials. The calculated results are compared with experiment.

<p>In this study, six dc Magnetron Sputtered (dcMS) CrN hard coatings were deposited on pretreated High Speed Steel (HSS) to achieve different interface architectures. The aim was to correlate the interfacial microstructure to the adhesion of the coatings. The substrates were pretreatment using the Ionized Physical Vapor Deposition (IPVD) method High Power Impulse Magnetron Sputtering (HIPIMS) using a Cr target in an inert atmosphere varying the substrate bias ($U_b$) between 0 V and 1100 V at ambient temperature as well as at a substrate temperature of 400$^\circ$C. The deposition parameters were chosen to show how kinetically induced diffusion, etching and implantation changes the interface chemistry and structure and to investigate their effect on the adhesion on the film. At elevated temperatures, the diffusion will be thermally driven. Annealing of the deposited samples were, therefore, performed at 900 K in an Ar atmosphere. The films were characterized employing XRD, HR-TEM, A-STEM and by scratch test measurements to see how the the interface microstructure can be correlated to the adhesion of the coating. The study shows that a sputter cleaned substrate surface with well preserved crystal structure of the substrate enhances the adhesion of the coating by promotion of local epitaxial growth. However, annealing was also shown to have a large effect on the adhesion enhancement by allowing for interdiffusion in the interface region and due to promotion of interface strain relaxation. Implantation of target material on the other hand had limited influence on the adhesion compared to the clean oxide free surfaces. The low adhesion improvement when gradually changing the chemical composition at the interface is assumed to stem from that the radiation induced defects and strain diminished the positive effect of this gradient.</p>

The aim of this Thesis was on one side to contribute to a better understanding of the phases formed in the TiAlSiN(O) system and the influence of impurities on their properties. On the other side it was also aimed in the Thesis to individually study the phases forming the nanocomposite. In each chapter the individual conclusions from that particular chapter are presented, a summary of the most relevant conclusions and achievements is listed below. ¡à Ti1-xAlxN(O) coatings The optical properties of Ti1-xAlxN(O) coatings were investigated. By changing the Al content in the coatings the properties change from the metallic character of TiN to dielectric character of AlN allowing to obtain spectrally selective coatings. For high Al content the films show low infrared reflectance and high emittance resulting in low equilibrium temperature, characteristics suitable for example for satellite temperature control. While the low emittance and high absorptance of low Al content are adequate for solar absorbers. The thermal stability of the low Al content coatings was investigated and the coatings are stable up to 400 ¨¬C without much change in the optical properties. ¡à SiyNz(O) coatings The silicon oxynitride coatings proved to be themselves interesting for their optical properties, specially the refractive index. The control of the microstructure was the key factor to control the optical properties of the coatings. Low energetic conditions in pure nitrogen atmosphere lead to the formation of closed porosity (nanovoids). The Raman results proved the encapsulation of nitrogen in the pores. Changing the N2 fraction in the gas mixture during deposition allows (at low power) to produce coatings with similar composition and mechanical properties presenting different refractive index by the introduction of the closed porosity. The closed porosity in the coatings is stable in N2 and vacuum up to 900 ¨¬C. Changing the target-substrate distance allows to produce coatings with different size of nanovoids. The possibility to extend the deposition of porous (close porosity) coatings to other systems is demonstrated. Porous silicon coatings were deposited by this method. ¡à nc-Ti1-xAlxN/a-SiyNz(O) coatings It was found from the XRD, SAED, EELS and XPS results, of coatings deposited under low energetic conditions, that the coatings are composed of a nanocrystalline cubic (Ti,Al)N phase embedded in an amorphous silicon oxynitride phase. The presence of oxygen impurities was identified particularly in non biased samples and estimated to be around 10 at% as the upper limit in these particular samples. Oxygen seems to be outside the nitride nanocrystallites, and mainly bond to silicon, forming amorphous silicon oxynitride phases and confirmed to occupy preferentially nitrogen positions (confirmed by HAADF and EFTEM) at the column boundaries. The application of substrate bias and substrate heating during deposition proved to be very efficient in reducing the oxygen incorporation in the coatings originating also denser coatings with improved mechanical properties. The different energetic conditions (either kinetic or thermal) at which the coatings were exposed during growth and the consequently obtained structures express the need for growth models were the transitions between zones can be achieved by a combination of substrate bias and substrate temperature.

In this study, six dc Magnetron Sputtered (dcMS) CrN hard coatings were deposited on pretreated High Speed Steel (HSS) to achieve different interface architectures. The aim was to correlate the interfacial microstructure to the adhesion of the coatings. The substrates were pretreatment using the Ionized Physical Vapor Deposition (IPVD) method High Power Impulse Magnetron Sputtering (HIPIMS) using a Cr target in an inert atmosphere varying the substrate bias ($U_b$) between 0 V and 1100 V at ambient temperature as well as at a substrate temperature of 400$^\circ$C. The deposition parameters were chosen to show how kinetically induced diffusion, etching and implantation changes the interface chemistry and structure and to investigate their effect on the adhesion on the film. At elevated temperatures, the diffusion will be thermally driven. Annealing of the deposited samples were, therefore, performed at 900 K in an Ar atmosphere. The films were characterized employing XRD, HR-TEM, A-STEM and by scratch test measurements to see how the the interface microstructure can be correlated to the adhesion of the coating. The study shows that a sputter cleaned substrate surface with well preserved crystal structure of the substrate enhances the adhesion of the coating by promotion of local epitaxial growth. However, annealing was also shown to have a large effect on the adhesion enhancement by allowing for interdiffusion in the interface region and due to promotion of interface strain relaxation. Implantation of target material on the other hand had limited influence on the adhesion compared to the clean oxide free surfaces. The low adhesion improvement when gradually changing the chemical composition at the interface is assumed to stem from that the radiation induced defects and strain diminished the positive effect of this gradient.