Nióbio e suas ligas são utilizados atualmente em muitas aplicações industriais por oferecerem excelente resistência à degradação em diversos meios corrosivos. Estes meios incluem atmosferas gasosas em temperaturas elevadas, como as encontradas em plantas de gaseificação de carvão existentes em usinas termelétricas para geração de energia. As atmosferas encontradas nestes meios são misturas gasosas complexasque contêm, entre outros compostos, oxigênio e enxofre. Os sulfetos são compostos menos estáveis, possuem pontos de fusão mais baixos e apresentam, freqüentemente, maiores desvios de estequiometria em relação ao óxido correspondente. Apesar de existirem estudos relacionados à aplicação de metais refratários em atmosferas sulfetantes a temperaturas elevadas, o uso de compostos de nióbio ainda não foi devidamente avaliado como revestimento protetor, havendo poucos dados disponíveis na literatura. O objetivo deste trabalho foi avaliar o efeito proporcionado por um filme de nióbio, obtido por pulverização catódica,sobre o comportamento de sulfetação isotérmica das ligas Fe-20Cr e Fe-20Cr-1Y.Os testes de sulfetação foram realizados a 500, 600 e 700°C pelo período de 2h em atmosfera H2/2%H2S. A avaliação da resistência à sulfetação foi feita por meio do ganho de massa por unidade de área exposta. Observou-se que o comportamento de sulfetação a 500ºC das ligas FeCr e FeCrY sem e com revestimento é similar. Nesta condição, nenhuma das ligas sofreu escamação. A 700ºC a liga FeCr sofreu leve escamação na forma de um pó fino, enquanto que o produto de reação formado sobre a liga FeCrY escamou na forma de placas. O efeito do nióbio se torna pronunciado a 700ºC. A camada de produto de reação formada sobre as ligas revestidas é mais fina e plástica que na liga sem revestimento. O ganho de massa por unidade de área diminuiu sensivelmente para as ligas recobertas, que não sofreram escamação. / Niobium and niobium based alloys are currently used in many industrial applications because they offer excellent resistance to degradation in various corrosive environments. These media include gaseous atmospheres at high temperatures such as those found in existing coal gasifying plants in power plants for energy generation. These atmospheres are complex gas mixtures that contain sulfur and oxygen, among other compounds. Sulphides are thermodynamically less stable, have lower melting points and often have larger deviations from stoichiometry compared to the corresponding oxides. Although there are studies regarding the use of refractory metals in high temperature sulphidizing atmospheres, the use of niobium compounds has not been adequately evaluated and there is very little studies available in the literature about its use as a protective coating. The aim of this study was to evaluate the effect of a niobium film, deposited by magnetron sputtering on the isothermal sulphidation behavior of Fe-20Cr and Fe-20Cr-1Y alloys. The sulphidation tests were carried out at 500, 600 and 700° C for 2h in H2/2% H2S atmosphere. The sulphidation resistance was determined by mass gain per unit area. The sulphidation behavior of the coated and uncoated alloys was similar at 500ºC, and none of the alloys spalled. At 700ºC FeCr alloy scalled in the form of a fine powder, while the reaction product formed on the alloy FeCrY scalled in the form of plates. The effect of niobium became pronounced at 700°C. The reaction product layer formed on the coated alloy was thinner andmore plastic than that formed on the uncoated alloy. The mass gain per unit area of the coated alloys decreased significantly and they did not scaled.

O PVD (Physical Vapor Deposition- Deposição física na fase de vapor) é um meio utilizado para a produção de recobrimentos e empregado em grande escala industrial. É um processo de deposição atômica no qual o material é vaporizado de alvo sólido por sputtering e posteriormente condensado sobre a peça a ser revestida na forma de filme. O processo ocorre em uma câmara de vácuo, na presença de plasma, e por diferença de potencial os íons, na forma pura ou combinados com átomos de hidrogênio ou carbono, são movidos para a superfície do substrato. Uma técnica relativamente nova de sputtering é o HiPIMS (High Power Impulse Magnetron Sputtering) que utiliza impulsos de energia extremamente altas com densidade de potência possibilitando filmes com melhores performances e mais densos. No presente trabalho filmes de nitreto de cromo (CrN) foram depositados por duas técnicas de magnetron sputtering, HiPIMS e DCMS (Direct Current Magnetron Sputtering), variando frequência de pulso em 400 Hz, 450 Hz e 500 Hz para o HiPIMS e a tensão de polarização em 0 V, -20 V, -40V, -60V, - 100 V e -140 V para os dois processos. Foram obtidos filmes com maior dureza, menor rugosidade para HiPIMS, no entanto DCMS apresentou maior taxa de deposição. O aumento da frequência nos filmes HiPIMS, assim como o aumento da tensão de polarização negativa possibilitaram filmes com morfologia mais densa e homogênea. Este fato também foi observado com o aumento do valor de bias nos filmes depositados por DCMS. Os valores de dureza obtidos (17 ± 2 para DCMS e 26 ± 1 para HiPIMS) são superiores aos reportados na literatura e podem estar relacionados ao efeito de \"multicamadas\" obtido pela oscilação do substrato. / PVD (Physical Vapor Deposition) is a process used for coatings deposition and it is used on a large industrial scale. It is an atomic deposition process in which the material is vaporized from solid target by sputtering and then condensed onto the part to be coated in film form. The process occurs in a vacuum chamber in the presence of plasma, and by potential difference the ions in pure form or combined with hydrogen or carbon atoms are moved to the surface of the substrate. A relatively new sputtering technique is the HiPIMS (High Power Impulse Magnetron Sputtering) which uses extremely high energy pulses with power density to enable higher performance and denser films. In the present work, chromium nitride (CrN) films were deposited by two magnetron sputtering techniques, HiPIMS and DCMS (Direct Current Magnetron Sputtering), varying the pulse frequency at 400 Hz, 450 Hz and 500 Hz for the HiPIMS and the bias at 0 V, -20 V, -40 V, -60 V, -100 V and -140 V for both processes. It was obtained films with high hardness, less roughness for HiPIMS, however DCMS presented a higher rate of deposition. The increase of the frequency in the HiPIMS films, as well as the increase of the negative polarization voltage, allowed films with denser and homogeneous morphology. This fact was also observed with the increase of the value in the films deposited by DCMS. The hardness values obtained (17 ± 2 for DCMS and 26 ± 1 for HiPIMS) were higher than those reported in the literature and may be related to the \"multilayer\" effect obtained by substrate oscillation.

Nióbio e suas ligas são utilizados atualmente em muitas aplicações industriais por oferecerem excelente resistência à degradação em diversos meios corrosivos. Estes meios incluem atmosferas gasosas em temperaturas elevadas, como as encontradas em plantas de gaseificação de carvão existentes em usinas termelétricas para geração de energia. As atmosferas encontradas nestes meios são misturas gasosas complexasque contêm, entre outros compostos, oxigênio e enxofre. Os sulfetos são compostos menos estáveis, possuem pontos de fusão mais baixos e apresentam, freqüentemente, maiores desvios de estequiometria em relação ao óxido correspondente. Apesar de existirem estudos relacionados à aplicação de metais refratários em atmosferas sulfetantes a temperaturas elevadas, o uso de compostos de nióbio ainda não foi devidamente avaliado como revestimento protetor, havendo poucos dados disponíveis na literatura. O objetivo deste trabalho foi avaliar o efeito proporcionado por um filme de nióbio, obtido por pulverização catódica,sobre o comportamento de sulfetação isotérmica das ligas Fe-20Cr e Fe-20Cr-1Y.Os testes de sulfetação foram realizados a 500, 600 e 700°C pelo período de 2h em atmosfera H2/2%H2S. A avaliação da resistência à sulfetação foi feita por meio do ganho de massa por unidade de área exposta. Observou-se que o comportamento de sulfetação a 500ºC das ligas FeCr e FeCrY sem e com revestimento é similar. Nesta condição, nenhuma das ligas sofreu escamação. A 700ºC a liga FeCr sofreu leve escamação na forma de um pó fino, enquanto que o produto de reação formado sobre a liga FeCrY escamou na forma de placas. O efeito do nióbio se torna pronunciado a 700ºC. A camada de produto de reação formada sobre as ligas revestidas é mais fina e plástica que na liga sem revestimento. O ganho de massa por unidade de área diminuiu sensivelmente para as ligas recobertas, que não sofreram escamação. / Niobium and niobium based alloys are currently used in many industrial applications because they offer excellent resistance to degradation in various corrosive environments. These media include gaseous atmospheres at high temperatures such as those found in existing coal gasifying plants in power plants for energy generation. These atmospheres are complex gas mixtures that contain sulfur and oxygen, among other compounds. Sulphides are thermodynamically less stable, have lower melting points and often have larger deviations from stoichiometry compared to the corresponding oxides. Although there are studies regarding the use of refractory metals in high temperature sulphidizing atmospheres, the use of niobium compounds has not been adequately evaluated and there is very little studies available in the literature about its use as a protective coating. The aim of this study was to evaluate the effect of a niobium film, deposited by magnetron sputtering on the isothermal sulphidation behavior of Fe-20Cr and Fe-20Cr-1Y alloys. The sulphidation tests were carried out at 500, 600 and 700° C for 2h in H2/2% H2S atmosphere. The sulphidation resistance was determined by mass gain per unit area. The sulphidation behavior of the coated and uncoated alloys was similar at 500ºC, and none of the alloys spalled. At 700ºC FeCr alloy scalled in the form of a fine powder, while the reaction product formed on the alloy FeCrY scalled in the form of plates. The effect of niobium became pronounced at 700°C. The reaction product layer formed on the coated alloy was thinner andmore plastic than that formed on the uncoated alloy. The mass gain per unit area of the coated alloys decreased significantly and they did not scaled.

Neste trabalho, foram produzidos filmes finos de carbono pela técnica de magnetron sputtering usando substratos monocristalinos de alumina com plano-c orientado em (0001) e substratos de Si (111) e Si (100), empregando Co, Ni e Cu como filmes intermediários (buffer-layers). As deposições foram conduzidas em três etapas, sendo primeiramente realizadas com buffer-layers de cobalto em substratos de alumina, onde somente após a produção de grande número de amostras, foram então realizadas as deposições usando buffer-layer de cobre em substratos de Si. Em seguida foram realizadas as deposições com buffer-layers de níquel em substratos de alumina. A cristalinidade dos filmes de carbono foi avaliada por meio da técnica de espectroscopia Raman e complementarmente por difração de raios X (DRX). A caracterização morfológica dos filmes foi feita por meio da microscopia eletrônica de varredura (MEV E FEG-SEM) e microscopia eletrônica de transmissão de alta resolução (HRTEM). Picos de DRX referentes aos filmes de carbono foram observados apenas nos resultados das amostras com buffer-layers de cobalto e de níquel. A espectroscopia Raman mostrou que os filmes de carbono com maior grau de cristalinidade foram os produzidos com substratos de Si (111) e buffers de Cu, e com substratos de alumina com buffer-layers de Ni e Co, tendo este último uma amostra com o maior grau de cristalinidade de todas as produzidas no trabalho. Foi observado que o cobalto possui menor recobrimento sobre os substratos de alumina quando comparado ao níquel. Foram realizados testes de absorção de íons de Ce pelos filmes de carbono em duas amostras e foi observado que a absorção não ocorreu devido, provavelmente, ao baixo grau de cristalinidade dos filmes de carbono em ambas amostras. / In this work, carbon thin films were produced by the magnetron sputtering technique using single crystal substrates of alumina c-plane (0001) and Si (111) and Si (100) substrates, employing Co, Ni and Cu as intermediate films (buffer-layers). The depositions were conducted in three stages, first with cobalt buffer-layers where only after the production of a large number of samples, the depositions using cooper buffer-layers were carried out on Si substrates. Then, depositions were performed with nickel buffer-layers using single-crystal alumina substrates. The crystallinity of the carbon films was evaluated by using the technique of Raman spectroscopy and, complementarily, by X-ray diffraction (XRD). The morphological characterization of the films was performed by scanning electron microscopy (SEM and FEG-SEM) and high-resolution transmission electron microscopy (HRTEM). The XRD peaks related to the carbon films were observed only in the results of the samples with cobalt and nickel buffer-layers. The Raman spectroscopy showed that the carbon films with the best degree of crystallinity were the ones produced with Si (111) substrates, for the Cu buffers, and sapphire substrates for the Ni and Co buffers, where the latter resulted in a sample with the best crystallinity of all the ones produced in this work. It was observed that the cobalt has low recovering over the alumina substrates when compared to the nickel. Sorption tests of Ce ions by the carbon films were conducted in two samples and it was observed that the sorption did not occur probably because of the low crystallinity of the carbon films in both samples.

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.

<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.

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>