In this work columnar nanospirals of AlInN were grown on top of TiN-coated sapphire substrates by magnetron sputtering. A variety of samples with different growth parameters were fabricated and investigated. The main objectives in this work were to optimize the degree of circular polarization and to control the active wavelength region for where this polarization effect occurs. Attempts were made to achieve a high degree of circular polarization in both reflected and transmitted light. It is shown that for reflected light it is possible to achieve a high degree of circular polarization within the visible wavelength regions. For transmitted light the concept of achieving circularly polarized light is proven.

Darbe tiriamas magnetroniniu plazminiu būdu suformuotų Mg-Al-Zr lydinių anodinis tirpimas, bei antikorozinės savybės. Magnetroniniu plazminiu būdu buvo suformuotos dangos su skirtingu cirkonio kiekiu (t.y. 95%, 90,4%, 76,2%, 71% ir 67%). Dangos formuojamos ant stiklo paviršiaus. Voltamperiniais ir elektrocheminio impedanso metodais ištirtas Mg-Al-Zr lydinių anodinis atsparumas ir korozinė elgsena 0.1 M (NH4)3BO3 + 0.1 M NaCl tirpale, kurio pH 8,5. MP lydinių korozinis atsparumas didėja, didinant Zr koncentraciją lydinyje. Taip pat lydiniai, kuriuose didesnė Mg koncentracija, bet mažesnė Zr aktyviai anodiškai tirpsta. Atominės jėgos mikroskopo metodu (AJM) nustatyta lydinių morfologija, dangos su didesne Zr koncentracija charakterizuojamos mažesniais kristalitų dydžiais. Aptartos MP metodo pritaikymo galimybės. / The goal of this work was to study anodic dissolution and anticorrosion properties of Mg-Al-Zr alloys formed by magnetron sputtering. Magnetron sputtering technique was applied to deposit Mg-Al-Zr alloys with different amount of Zr, on glass substrates. Anodic dissolution and anticorrosive stability of the sputtered alloys were studied by voltammetric and electrochemical impedance spectroscopy methods in 0.1 M (NH4)3BO3 + 0.1 M NaCl solution (pH 8,5). EIS and voltammetric measurements indicated a lesser anodic dissolution and a superior anticorrosive resistance in Mg-Al-Zr alloys with higher Zr concentration. Atomic force microscopy demonstrated (AFM) that by increasing amount of Zr in sputtered samples the grain size decrease.

Darbe tiriamos magnetroniniu plazminiu (MP) būdu suformuotų Mg – Al – Zr lydinių morfologinės, korozinės ir puslaidininkinės savybės. Magnetroninio plazminio dulkinimo metodu buvo suformuotos 5Mg-Al-95Zr, 33Mg-Al-67Zr, 29Mg-Al-71Zr, 24Mg-Al-76Zr, 8Mg-Al-90Zr dangos ant stiklo paviršiaus. Atominės jėgos mikroskopo (AJM) metodu nustatyta, kad magnetroniniu plazminiu būdu suformuotos Mg – Al – Zr lydinių dangos charakterizuojamos mažesniais kristalitų dydžiais ir tolygesne mikrostruktūra. Fotoelektrocheminiais ir elektrocheminio impedanso spektroskopijos metodais ištirta lydinių korozinė elgsena 0,1 M (NH4)3BO3 + 0,1 M NaCl ( pH = 8,5) tirpale. Mott – Shottky analizės metodu nustatytas puslaidininkinių paviršiaus sluoksnių laidumo pobūdis: 5Mg-Al-95Zr, 33Mg-Al-67Zr, 29Mg-Al-71Zr, 24Mg-Al-76Zr, 8Mg-Al-90Zr dangų atveju jis donorinis (n – tipo). Aptartos Mott – Shottky metodo taikymo magnetroninėms dangoms tirti galimybės. / The aim of present work was to study corrosion properties of magnetron sputtered Mg – Al – Zr alloys and characterise semiconductor properties of the surface layers developed during corrosion. Atomic force microscopy (AFM) demonstrated, that sputtered alloys had a smaller grain size and a smoother surface. Fotocorrosion and electrochemical behaviour of tha alloys was studied in 0,1 M (NH4)3BO3 + 0,1 M NaCl ( pH = 8,5) solution. The Mott – Schottky plots of 5Mg-Al-95Zr, 33Mg-Al-67Zr, 29Mg-Al-71Zr, 24Mg-Al-76Zr, 8Mg-Al-90Zr electrodes showed a linear relationship between modified capacitance (C-2) on applied potential. It was concluded n – type semiconductivity for the layers on 5Mg-Al-95Zr, 33Mg-Al-67Zr, 29Mg-Al-71Zr, 24Mg-Al-76Zr, 8Mg-Al-90Zr alloys.

Recent studies of fcc metals with dense twins (~10 nm spacing) have revealed impressive mechanical properties, along with improved ductility and electrical conductivity in comparison to nanocrystalline metals with similar feature sizes. Many important fcc metals could benefit from these “nanotwinned” microstructures, however, not all fcc metals readily form such twins. The tendency of fcc metals to form twin boundaries is related to the twin boundary energy; those with low twin boundary energy, such as silver (Ag), easily form twins. Increasing twin boundary energy interferes with twin formation, to the point that in metals with high twin boundary energy, like aluminum (Al), twins are quite rare. This thesis focuses on the synthesis of nanotwinned Ag and Al via physical vapor deposition. Nanotwinned Ag is readily fabricated, however, a template approach had to be developed to induce twins in Al. The microstructures and their relationships to observed mechanical properties are also discussed. Grain boundaries interfere with dislocation transmission by posing a slip system discontinuity between grains. Twin boundaries are a special class of grain boundaries in which the grains on either side of the boundary are related by mirror symmetry. Twin boundaries inhibit dislocation transmission, providing strength in the same manner as grain boundaries. However, their symmetrical structure reduces the free volume and grain boundary energy. Accordingly, coherent twin boundaries are often more energetically stable than grain boundaries, and their coherency allows plasticity mechanisms to remain active under conditions where such mechanisms may be inhibited at grain boundaries. Hence, twin boundaries may provide a metal with unique combinations of high strength and good ductility, conductivity, and thermal stability.

This thesis present research on synthesis, microstructure, and properties of carbide- and boride- based thin films. The films have been synthesized by dc magnetron sputtering, and their microstructures have been characterized mainly by X-ray photoelectron spectroscopy (XPS), X-ray diffraction, and transmission electron microscopy.  One of the main objectives with this research has been to evaluate the thin films potential as materials for sliding electrical contact applications and this have influenced, which properties that have been evaluated. Co-sputtered Nb-C films have a microstructure comprising of nanocrystalline NbCx  (nc-NbCx) grains embedded in a matrix of amorphous C (a-C). A thinner a-C matrix form in the Nb-C films compared to the well-studied Ti-C system. As a consequence, the Nb-C films have a higher hardness and conductivity than previously studied Ti-C sputtered under similar conditions. The promising electrical contact properties are attained for reactively sputtered Nb-C films under industrial conditions, at deposition rates two orders of magnitude higher. A reduction in crystallinity is seen when Si is added to the Nb-C films and amorphous films forms at Si content > 25 at.%. The alloying of Si was however not beneficial for the electrical contact properties. Substoichiometric CrB2-x (B/Cr = 1.5) and NbB2-x (B/Nb = 1.8) films are achieved when deposited from MeB2 targets. Boron segregates to grain boundaries forming a B-rich tissue phase. This result in superhardness for the NbB2-x films (42 ± 4 GPa) as well as a low friction attributed to the formation of a boric acid film. Carbon forms a solid solution in the MeB2 grains as well as segregating to grain boundaries forming an amorphous BCx (a-BCx) phase when alloyed to CrB2-x and NbB2-x films. The formation of the a-BCx phase drastically improves the electrical contact resistance of the NbB2-x films. However, the mechanical properties are degraded, which result in a high friction and wear rate. It was in TEM studies of the metastable amorphous structures for the Nb-Si-C films found that the electron beam induces crystallization. Hence, great care is required when studying these types of metastable structures.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / In this work a survey of the potentialities and limitations of magnetron sputtering as a tool for the production of MgB2 superconductors thin films has been made. Instead of the usual approaches, like co-deposition onto heated substract or room temperature deposition of MgB multilayers for ex situ annealing, the direct deposition of multilayers onto heated substract has been tested. The samples have been deposited onto Si waffers from Mg and B targets. They have been produced by the alternated grown of Mg and B layers, holding the substrate temperatur at 200 and 300 C during the depostion. Pos deposition annealings were performed at temperatures rangingo from 560 up to 800. In order to improve the sticking coefficient of Mg atoms at the substrate, the ayers thicknesses were held under ten monoatomic layers. The composition and structural properties were determined by X-Ray diffraction. The results have shown that, for the used temperatures, the Mg sticking coefficient onto B is just relevant ultil the second or third Mg monoatomic layer is completed. From this point, all Mg atoms impinging the substrate are re-emmitted to the chamber atmospherre. As a consequence, the direct production of MgB2 from the sucessive deposition of B and Mg are not effective, unless the layers thicknesses do not surpass a few tenths of nanometers. / Neste trabalho foram avaliadas as potencialidades e as limitações do "magnetron sputtering" como técnica de deposição de filmes finos de MgB2 supercondutores. No lugar das técnicas tradicionais, como a co-deposição em substrato aquecido ou a deposição de multicamadas para tratamentos térmicos ex-situ, foi testada a rotina de deposição de multicamadas diretamente sobre alvo aquecido, "in situ". As amostras foram depositadas sobre substratos de Si a partir de alvos de Mg e B. Elas foram obtidas pela deposição sucessiva e alternada de camadas de Magnésio e Boro, com temperaturas do substrato (in-situ) de 260oC e 300oC e ex-situ entre 560 e 800oC. Para aumentar a chance de fixação dos átomos de Mg no substrato já durante a deposição, as espessuras das camadas foram mantidas finas, com menos de uma dezena de planos atômicos. A composição e as propriedades estruturais das amostras produzidas foram analisadas a partir de difração de Raios-X. Os resultados obtidos mostram que, na faixa de temperatura usada, o coeficiente de fixação do Mg sobre o B é significativo apenas até que a segunda ou terceira camadas atômicas sejam concluídas. A partir deste ponto, todo o magnésio que atinge o substrato é re-emitido. Como consequência, a obtenção de MgB2 por sputtering na forma de multicamadas não é viável, pelo menos para espessuras maiores que décimos de nanometros.

Submitted by Ronildo Prado (ronisp@ufscar.br) on 2017-08-23T17:56:30Z No. of bitstreams: 1 DissPSS.pdf: 2648669 bytes, checksum: ac3f76c4b2b9666e9decfa0e9745dece (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-08-23T17:56:38Z (GMT) No. of bitstreams: 1 DissPSS.pdf: 2648669 bytes, checksum: ac3f76c4b2b9666e9decfa0e9745dece (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-08-23T17:56:44Z (GMT) No. of bitstreams: 1 DissPSS.pdf: 2648669 bytes, checksum: ac3f76c4b2b9666e9decfa0e9745dece (MD5) / Made available in DSpace on 2017-08-23T17:56:49Z (GMT). No. of bitstreams: 1 DissPSS.pdf: 2648669 bytes, checksum: ac3f76c4b2b9666e9decfa0e9745dece (MD5) Previous issue date: 2017-03-10 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / With the increase in life expectancy, there has been a raise in the use of prostheses due to the need to replace parts of the human body. To avoid tissue rejection, metal alloys from implants should be biocompatible. The Ti-6Al-4V alloy is widely used in prostheses, however, aluminum presents tissue irritation and inflammation issues and vanadium oxide is unstable, with a high probability of being cytotoxic. Thus, the search for new alternatives has reached the Ti-β alloys, whose properties are more similar to those of the human bone and its structure can present stable or metastable phases according to the quantity of the alloying elements. Unfortunately, Ti prosthesis have a high price compared to the 316L and 316L stainless steel ones, as the later do not have the biocompatibility characteristics of Ti. It seems an interesting research topic about how to use a Ti alloy coating in stainless steel for biomedical application. To be able to deposit the metal alloy, magnetron sputtering is a good choice, since this technique is largely used to obtain thin films due to the quality of the formed films, their high deposition rate, low pressure work and less intense electron bombardment of the substrate. Consequently, it has been used in the manufacture of thin films of Ti and its alloys for biomedical applications. There is no notice of another research group working in this theme. In this project, the objective is to study the influence of the surface change on the deposition of the thin films and if there is difference in the composition when performing chemical cleaning before spraying. / Com o aumento da expectativa de vida, houve um aumento no uso de próteses devido à necessidade de substituir alguma parte do corpo humano. As ligas metálicas utilizadas em implantes devem ser biocompatíveis, para evitar a rejeição pelo corpo. Uma liga muito utilizada é a Ti-6Al-4V, entretanto o alumínio possui problemas de irritação e inflamação de tecidos e o óxido de vanádio é instável, com alta probabilidade de ser citotóxico. Assim, a procura de novas alternativas chegou-se as ligas de Ti-β, cujas propriedades são mais parecidas com as do osso humano e sua estrutura pode apresentar fases estáveis ou metaestáveis de acordo com a quantidade dos seus elementos de liga. Entretanto, próteses de Ti tem um preço alto em relação as de aço inoxidável 316 e 316L. Como estas não possuem as características de biocompatibilidade do Ti, é interessante utilizar um recobrimento de liga de Ti em aço para uso biomédico. Para a deposição da liga metálica, o processo de pulverização magneto-catódica é de grande interesse. Essa técnica consagrou-se na deposição de filmes finos devido a sua alta taxa de deposição, trabalho a baixas pressões, bombardeamento menos intenso de elétrons no substrato e qualidade do filme formado. Consequentemente, passou a ser utilizada na fabricação de filmes finos de Ti e suas ligas para aplicações biomédicas. O objetivo deste projeto é estudar a influência da alteração da superfície na deposição dos filmes finos, ou seja, se há diferença na composição ao se realizar limpeza química antes da pulverização. É importante notar que não se tem notícia de outro grupo de pesquisa trabalhando no mesmo tema.

The doctoral thesis deals with the experimental study of the low-temperature plasma designated for the preparation of thin films using the method of physical sputtering. It describes measurements which were realized on two types of devices - on the low-pressure plasma jet sputtering system and on the planar magnetron. The plasma diagnostics in the discharge excited in the pulse regime represent the main theme of the thesis. The discharge in the low-pressure plasma jet was studied by means of an electrostatic Langmuir probe, in the case of the planar magnetron, mass spectroscopy with energetic as well as time resolution was used. To understand the results achieved in the pulse generated plasma good knowledge of the basic continuous DC regime of the discharge excitation is essential. Therefore a considerable part of the thesis deals purely with the continuous DC discharge. In the case of the low- pressure plasma jet, the attention was focused also on the characteristic property of this plasma source, which is the flow from the jet.

Novel type of catalyst for proton exchange membrane fuel cells anode is demonstrated. It is based on magnetron sputtered Pt-CeO2 a Pt-Sn-CeO2 mixed oxides. It is shown, that these materials allow to significantly decrease amount of platinum in the anode catalyst. The preparation method yields high amount of platinum in ionized form, especially Pt2+ , which is related to the high activity. Stability of these catalytic layers were investigated under conditions similar to fuel cell anode (humidified hydrogen at elevated temperature). Also interaction of hydrogen a water under UHV conditions were studied, demonstrating high stability of the Pt2+ species. In the last part of the work sputtered Pt-Co mixed catalyst were investigated to be used in the PEMFC cathode. It is demonstrated that at right conditions, the sputtered alloy catalyst improves mass activity on cathode by factor more than two.

Les oxydes conducteurs transparents (TCO) sont une classe importante de matériaux possédant de nombreux domaines d’application, telles que les revêtements à faible émissivité ou comme électrodes transparentes pour les panneaux photovoltaïques et écrans plats. Parmi les matériaux TCO possibles, le ZnO dopé à l'Al (AZO) est couramment étudié notamment à cause de son coût relativement faible et de l'abondance en matières premières des éléments qui le compose. Les films minces d'AZO sont généralement produits par l’intermédiaire de procédés de dépôts physiques en phase vapeur, tels que la pulvérisation cathodique magnétron. Cependant, l’une des limitations de ces techniques repose sur l’homogénéité des films en utilisant la pulvérisation magnétron réactive (DCMS). Ce problème d'homogénéité peut être lié au bombardement du film en croissance par des ions négatifs d'oxygène, lesquels peuvent induire la présence de défauts accepteurs supplémentaires et la formation de phases secondaires isolantes. Dans ce travail, les films d'AZO sont déposés par pulvérisation cathodique magnétron en régime d’impulsions haute puissance (HiPIMS), un procédé dans laquelle des densités de courant instantanées élevées sont obtenues par l’intermédiaire de courtes impulsions de faible rapport cyclique. Dans la première partie de cette thèse, la possibilité d'améliorer l'homogénéité des films AZO par HiPIMS est démontrée. Cette amélioration peut être liée à un important taux de pulvérisation instantanée pendant chaque impulsion HiPIMS, de sorte que le processus puisse avoir lieu en régime métallique. Ceci permet de réduire l’impact du bombardement en ions d'oxygène pendant la croissance du film, évitant ainsi la formation de phases secondaires. Un autre problème de l'AZO est la stabilité des propriétés intrinsèques dans des environnements humides. Pour évaluer ce problème, la dégradation des propriétés électriques après une procédure de vieillissement a été étudiée pour des films déposés à la fois par DCMS et HiPIMS. Une méthode a été proposée pour restaurer les propriétés des films qui consiste en un recuit à basse température sous atmosphère de N2. L'amélioration des propriétés électriques des films peut être liée à un processus de diffusion dans lequel l’eau est évacuée hors des films. Ensuite, l'influence de la température du substrat sur les propriétés des films d'AZO déposés par HiPIMS a été étudiée. Les propriétés électriques, optiques et structurelles ont été améliorées avec l'augmentation de la température du substrat jusqu'à 600°C. Cette amélioration peut s’expliquer par l'augmentation de la qualité cristalline et le recuit des défauts. Dans une dernière partie, le dépôt de films d'AZO sur des substrats flexibles de PET a été étudié. Les films se développent sous la forme d'une couche épaisse, poreuse et composés de colonnes orientées de manière préférentielle selon l’axe c au-dessus d’une fine couche de départ. L’analyse de la résistance électrique après déformation mécanique a permis de déterminer une relation de proportionnalité inverse ou la résistance électrique augmente avec la diminution du rayon de courbure, cette dernière étant moins prononcée pour des films plus épais / Transparent conducting oxides (TCOs) are an important class of materials with many applications such as low emissivity coatings, or transparent electrodes for photovoltaics and flat panel displays. Among the possible TCO materials, Al-doped ZnO (AZO) is studied due to its relatively low cost and abundance of the raw materials. Thin films of AZO are commonly produced using physical vapour deposition techniques such as magnetron sputtering. However, there is a problem with the homogeneity of the films using reactive direct current magnetron sputtering (DCMS). This homogeneity problem can be related to the bombardment of the growing film with negative oxygen ions, that can cause additional acceptor defects and the formation of insulating secondary phases. In this work AZO films are deposited by high power impulse magnetron sputtering (HiPIMS), a technique in which high instantaneous current densities are achieved by short pulses of low duty cycle. In the first part of this thesis, the possibility to improve the homogeneity of the deposited AZO films by using HiPIMS is demonstrated. This improvement can be related to the high instantaneous sputtering rate during the HiPIMS pulses, so the process can take place in the metal mode. This allows for a lower oxygen ion bombardment of the growing film, which can help to avoid the formation of secondary phases. Another problem of AZO is the stability of the properties in humid environments. To assess this problem, the degradation of the electrical properties after an aging procedure was investigated for films deposited by both DCMS and by HiPIMS. A method was proposed, to restore the properties of the films, using a low temperature annealing under N2 atmosphere. The improvement of the electrical properties of the films could be related to a diffusion process, where water is diffusing out of the films. Then, the influence of the substrate temperature on the properties of AZO films deposited by HiPIMS was studied. The electrical, optical and structural properties were found to improve with increasing substrate temperature up to 600°C. This improvement can be mostly explained by the increase in crystalline quality and the annealing of defects. Finally, the deposition of AZO films on flexible PET substrates was investigated. The films are growing as a thick porous layer of preferentially c-axis oriented columns on top of a thin dense seed layer. The evolution of the sheet resistance of the films after bending the films with different radii was studied. There is an increase in the sheet resistance of the films with decreasing bending radius, that is less pronounced for thicker films