Os objetivos gerais deste trabalho foram estudar o comportamento de densificação e as propriedades mecânicas do nitreto de alumínio (AlN) com aditivo de sinterização. Os objetivos específicos foram estudar: 1) o efeito do teor de Y2O3 na densificação do AlN; 2) o efeito da adição de carbono na densificação do AlN com CaO; 3) o efeito da adição simultânea de Y2O3 e CaO na densificação do AlN; 4) o efeito da porosidade nas propriedades elásticas do AlN com Y2O3 ou CaO; e 5) o efeito do teor de Y2O3 ou CaO nas propriedades mecânicas do AlN. As amostras foram sinterizadas sob atmosfera inerte em várias temperaturas (1100-2000ºC) e analisadas por determinação de densidade, difração de raios X e microscopia eletrônica de varredura. As propriedades determinadas à temperatura ambiente foram: constantes elásticas pelo método de pulso-eco ultra-sônico, resistência à flexão biaxial, dureza Vickers e tenacidade à fratura pelos métodos Indentation Fracture (KIc-IF) e Indentation Strength (KIc-IS). O AlN com Y2O3 apresentou significativa densificação por sinterização no estado sólido, mas completa densificação ocorreu somente por sinterização via fase líquida. A densificação do AlN não foi influenciada pelo aumento de 0,5% a 4% de Y2O3, pois a temperatura de formação da fase líquida (~ 1725ºC) não variou nesta faixa de teor de aditivo. Porém, a adição de carbono levou à formação de segundas-fases refratárias no AlN com 4% de Y2O3, o que atrasou sua densificação devido ao aumento da temperatura de formação da fase líquida. A adição de carbono não mudou a temperatura de formação da fase líquida do AlN com 4% de CaO sinterizado acima de 1650ºC, mas sua densificação também atrasou devido à diminuição da fração de fase líquida e ao aprisionamento de gás nos poros fechados. A adição simultânea de CaO e Y2O3 diminuiu significativamente a temperatura de sinterização do AlN em relação às adições individuais destes aditivos. O AlN com mistura de CaO e Y2O3 atingiu quase completa densificação a partir de 1650ºC devido à formação de fase líquida com composição próxima da fase CaYAl3O7, que apresentou boas características de molhamento e espalhamento nesta temperatura de sinterização. A adição de carbono mudou a composição das segundas-fases de CaYAl3O7 para CaYAlO4 e, então, para YAM (2Y2O3.Al2O3) no AlN com mistura de CaO e Y2O3, o que atrasou sua densificação em baixas temperaturas de sinterização (< 1700ºC) devido à alta viscosidade e/ou baixa molhabilidade da fase CaYAlO4 e à alta refratariedade da fase YAM. As propriedades elásticas, bem como a dureza Vickers do AlN foram influenciadas pela porosidade, mas não foram influenciadas pelo tipo (CaO e Y2O3) e teor (0,5% a 8% em massa) de aditivo de sinterização. A resistência 7 à flexão foi influenciada pelo tipo e teor de aditivo de sinterização, sendo observado um teor crítico de aditivo, acima do qual esta propriedade diminuiu significativamente e, então, tendeu a permanecer constante em função do teor de aditivo. Não se observou correlação entre tenacidade à fratura e resistência à flexão. Os valores de KIc-IS, que não variaram com o tipo e teor de aditivo de sinterização, foram considerados mais consistentes do que os valores de KIc-IF. / The general objectives of this work were to study the densification behavior and the mechanical properties of aluminum nitride (AlN) with sintering aid. The specific objectives studied were: 1) the effect of Y2O3 content on the densification of AlN, 2) the effect of carbon addition on the densification of AlN with CaO, 3) the effect of simultaneous addition of Y2O3 and CaO on the densification of AlN; 4) the effect of porosity on elastic properties of AlN with CaO or Y2O3, and 5) the effect of Y2O3 or CaO content on the mechanical properties of AlN. The samples were sintered under inert atmosphere at various temperatures (1100ºC-2000ºC) and analyzed by density measurement, X-ray diffraction and scanning electron microscopy. The properties measured at room temperature were: elastic constants by the ultrasound pulse-echo method, biaxial flexural strength, Vickers hardness and fracture toughness by the Indentation Fracture (IF) and Indentation Strength (IS) methods. AlN with Y2O3 presented significant densification by solid-state sintering, but full densification occurred only by liquid-phase sintering. The densification of AlN was not influenced by the increase of 0.5% to 4% Y2O3, since the liquid-phase formation temperature (~ 1725ºC) did not change in this range of additive content. However, the addition of carbon to AlN with 4% Y2O3 led to formation of refractory second-phases, which delayed the densification due to an increase of the liquid-phase formation temperature. The addition of carbon did not change the liquid-phase formation temperature of AlN with 4% CaO sintered above 1650ºC, but its densification delayed significantly due to the diminution of liquid-phase fraction and trapped gas in closed pores. The simultaneous addition of CaO and Y2O3 significantly diminished the sintering temperature of AlN in relation to the individual additions of these additives. AlN with simultaneous addition of CaO and Y2O3 achieved almost full densification at 1650ºC due to formation of liquid-phase with composition close to CaYAl3O7 phase, which had good wetting and spreading characteristics at this temperature. The addition of carbon changed the composition of second-phases from CaYAl3O7 to CaYAlO4 and then to YAM (2Y2O3.Al2O3) in AlN with simultaneous addition of CaO and Y2O3, delaying its densification at low sintering temperatures (< 1700ºC) due to the high viscosity and/or low wettability of CaYAlO4 phase and high refractoriness of YAM phase. The elastic properties, as well as Vickers hardness were influenced by the increase of porosity, but were not influenced by type (CaO and Y2O3) and content (0.5% to 8% in mass) of sintering aid. Flexure strength was influenced by the type and content of sintering aid. It was observed a critical additive content, 9 above which the strength decreased significantly and then tended to remain almost constant as a function of additive content. No relationship was observed between fracture toughness and flexure strength. The KIc-IS values, which did not vary with type and content of sintering aid, were found to be more consistent than the KIc-IF values.

Les cristaux dopés par des ions de terre rare (TR) apparaissent prometteurs pour des applications dans le traitement quantique de l'information. Parmi ces matériaux, les cristaux massifs d'Eu3+:Y2O3 présentent un long temps de cohérence optique (T2), un paramètre fondamental pour les technologies quantiques. Ce travail de thèse porte sur l'étude de ce système à l'échelle nanométrique, ce qui pourrait permettre de développer des systèmes hybrides dans lesquels les TR sont couplées à d'autres systèmes quantiques. Des nanocristaux de différentes tailles ont été élaborés par précipitation homogène. La largeur optique inhomogène diminue avec des recuits à haute température et peut atteindre les valeurs mesurées dans des cristaux massifs. Une corrélation quasi-linéaire avec les largeurs de raie Raman a aussi été observée. Les temps de vie de population sont plus longs que dans les échantillons massifs et peuvent être modélisés par un indice de réfraction effectif. Les T2 optiques ont ensuite été déterminés par écho de photon et creusement de trou spectral. Nous avons mesuré un temps de cohérence de 7.1 µs à 1.7 K dans un échantillon dopé à 0.5 % en Eu3+, la valeur la plus élevée observée pour un nanocristal. Une étude en température et de la diffusion spectrale indique que le déphasage est dominé par des fluctuations de la structure et des basculements de spins. / Rare earth (RE) doped crystals are promising materials for quantum information processing (QIP). In particular, Eu3+:Y2O3 bulk crystals present long optical coherent lifetimes (T2), a fundamental parameter for QIP. In this thesis, we investigated this system at the nanoscale, which could be used to build hybrid devices where RE are coupled to other quantum systems. This work focuses on the development of Eu3+: Y2O3 particles with sub-wavelength size and on the static and dynamical contributions to Eu3+ optical linewidth. Systems with different particle and crystallite sizes were prepared using homogeneous precipitation. Optical inhomogeneous linewidths were found to decrease with high temperature annealing and reached values close to those of bulk crystals, showing that low defect concentrations can be obtained. A quasi-linear correlation with Raman linewidths was also observed. T1 population decays were measured by fluorescence and found longer than in the bulk, in good agreement with a model based on an effective refractive index model. Optical T2 were investigated by photon echo (PE) and holeburning techniques. We observed a coherence lifetime of 7.1 µs at 1.7 K in a 0.5 % Eu3+ doped sample, the highest value reported for any nanocrystal. Temperature dependence and spectral diffusion studies indicate that structure fluctuations and spin flips dominate dephasing.

Processing of Bulk Metastable Oxide Ceramics Oxide ceramic materials are extensively used in various modern application domains which require properties such as high temperature stability or creep resistance, wear resistance, chemical stability, useful electronic, optical and magnetic properties. In the diverse arena of materials technology that interlinks processing, structure, properties and performance, the advancement of new processing techniques to develop oxide ceramics facilitates the extension and refinement of their desirable properties and also mitigate their limitation in terms of application. Progress in processing science/technology offers a real impetus to the development of metastable ceramics with novel, non-equilibrium structures that exhibit scientifically interesting properties and have the potential to cater to the requirements of modern application areas. In the absence of the equilibrium state of a material system, metastable states can be formed with amorphous phases, extended solid solutions, metastable crystal structures and nanocrystallinity. Such metastable states can be retained by imposing kinetic constraints, which means that under the conditions of temperature and pressure, atomic mobilities are inadequate for the transformation. Metastable ceramics that are produced using non-equilibrium processing routes, such as rapid solidification, vapour deposition, spray pyrolysis, sol-gel technique etc., have been known to possess potentially useful properties, such as hard and soft magnetic characteristics, semiconductivity, varistor action, optical transmittivity and superconductivity. Apart from possessing attractive properties, a metastable phase may also serve as a precursor to a desired microstructure; for instance, controlled crystallization of an amorphous phase is a possible way enroute to nanocrystalline structure. It was well recognized that the comprehensive study and use of nanostructured and other metastable ceramics requires consolidation of the fine discontinuous forms (powders or flakes) produced from non-equilibrium processing routes, into bulk shapes with greater control on the fine scale of the structure. Such efforts have not been entirely successful. Non-equilibrium processing techniques do not produce the metastable materials in bulk form. Consolidation of metastable ceramics into dense forms needs high temperatures, mechanical activation (in the form of static pressures or shock waves), or a combination of both. Such activation may trigger the transformation of the desired metastable phase into a more stable phase with concurrent grain growth. Conversely, conditions that allow the desired metastable phase to be retained may not be adequate for complete densification. The subject of the present thesis is two-fold: (i) processing of dense amorphous Al2O3-Y2O3 materials through a novel densification route involving hot pressing of amorphous powders, produced by co-precipitation, at low temperatures and moderately high pressures, (ii) detail study of possible deformation mechanisms of the amorphous phase from mechanical testing at elevated temperatures. Unusual deformation behavior of the bulk amorphous material has been related to the densification process. Development of Pressure Consolidation Technique Amorphous powder of composition Al2O3-15 mol% Y2O3 (A15Y) was synthesized by co-precipitating a hydroxide from metal nitrate precursor’s solution by using ammonium hydroxide. Chemical homogeneity was ensured by a molecular level mixing of precursors of aluminium and yttrium at room temperature. The as-precipitated powder undergoes thermal decomposition (pyrolysis) to an amorphous oxide by ~770-800o C. The crystallization temperature was found from thermal analysis to be ~900o C, with γ-Al2O3 as the initial product of crystallization. The true density of the amorphous A15Y phase was measured to be only 2.69 g cm-3 by pycnometry, which is ~2/3 of the assemblage of equilibrium crystalline phases consisted of Al2O3 and YAG. Uniaxial hot pressing was performed with decomposed, classified powders (large agglomerates with sizes more than 10 µm were removed by sedimentation technique) at low temperature of about 630-640o C and moderately high pressure of 710-750 MPa. Pressure was held constant for 30-45 minutes. Cold compaction at pressures of 50-65 MPa for 8-10 minutes was carried out prior to hot pressing to ensure green strength of the compacts. All hot-pressed compacts revealed significant densification (95-96% relative densities) with uniformly distributed fine porosity. X-ray diffraction, electron microscopy analysis, Raman spectroscopy and differential thermal analysis established the amorphous nature of the dense, hot-pressed pellets. The amorphous phase displays an elastic modulus of ~ 50-60 GPa and a hardness of 4-5 GPa, which are considerably lower than those of the crystalline counterpart. Deformation Behavior of Amorphous Al2O3-Y2O3 The experiments described above clearly demonstrated the feasibility of producing bulk metastable ceramics in the Al2O3-Y2O3 system by a novel consolidation (viz., low temperature-high pressure) route of amorphous powders. This section of the thesis concentrates on studying the deformation mechanisms of the amorphous phase, which are found to be characteristic of the temperature domain of the experiment. Uniaxial compression tests at temperatures of 650-850o C with constant engineering strain rates of ~3-4 X 10-4 s-1 were conducted on dense amorphous samples made from the hot-pressed compacts. At a temperature of 850o C, i.e., close to the crystallization temperature, the amorphous phase was characterized by homogeneous deformation with continuous work hardening after yielding, accompanied by an increase in the true density of this glass by 10-12%. X-ray and electron microscopy analysis confirmed that the density increase was not due to the formation of nano-crystals at this high temperature. Raman spectroscopy and differential thermal analysis further corroborates that the glass was amorphous even after deformation. No shear instabilities were formed at the side surfaces due to the deformation. Significantly large compressive longitudinal strains up to about 28% were observed before unloading. Moreover, an interrupted loading-unloading test established that the bulk density increase was monotonic with the existence of multiple amorphous states enroute to a succession of denser structures. A simultaneous increase in both hardness (H) and modulus (E) of the amorphous phase of up to 100% after deformation bolstered this experimental observation of bulk density increment at constant porosity. The above evidence clearly points towards significant structural changes of the amorphous phase during high temperature deformation process and therefore a phenomenon of molecular densification of the amorphous structure through a hierarchy of dense amorphous phases was hypothesized, analogous to density or entropy driven amorphous-to-amorphous phase transitions (polyamorphism). Note that the densification described here does not refer to the conventional removal of porosity in a ceramics. At an intermediate temperature of 725o C, which is significantly (~200o C) below the crystallization temperature, plastic deformation commences at a stress (yield stress) of 700-780 MPa (considerably higher compared to the yield stress at 850o C) and continued to deform plastically with a slowly decreasing flow stress before reaching a plateau. Thus, the glass exhibited flow softening, in contrast to flow hardening observed at 850oC. Plastic deformation of this glass is largely non-viscous through shear instabilities (akin to the low temperature deformation behavior of metallic glass) and resulted in 8% increment in bulk density after deformation. Once again, the amorphous nature of the glass after deformation was confirmed by X-ray and electron microscopy analysis. Therefore, this intermediate temperature domain was characterized by both densification and shear. Deformation at even lower temperature, viz., at the temperature of hot pressing (650o C), was also characterized by elastic-plastic behavior (similar to flow softening described above), with immediate yield drop after yielding and resulted in a fairly large amount of plasticity of about 17% before unloading. The bulk density was found to be increased only by 2%. Another very interesting experimental finding from the present investigation is the time-dependent deformation (viz., creep densification) exhibited by this glass. It was established from the result of longer term creep experiment at 850o C that the glass revealed large uniaxial compression of about 15% with 5.5% densification to a density of 3.02 g cm-3. Strain rate sensitivity of the A15Y glass was revealed by another stress jump test. To summarize, the present thesis elucidates the discovery of a new class of ceramics with unusual physical properties in an amorphous mixture of Al2O3-Y2O3, which is in contrast to the conventional brittle ceramics. This new class of ceramics deforms plastically without any hydrostatic containment, like ductile metal, at temperatures about 1000o C below those at which their crystalline counterpart would deform. The behavior of this amorphous ceramics under stress that leads to unusually large change in shape, density, hardness and modulus with hierarchies of amorphous structures is demonstrated in detail with experimental evidence.

This thesis presents a Microwave Plasma Assisted Spray Deposition (MPASD) system design, characterization, and application to produce nano-sized particle coatings of metal oxides. A commercially available rectangular waveguide microwave power delivery system is utilized to initiate and sustain the plasma discharge within the customized plasma applicator where micron-sized droplets of a metal ion solution are heated to evaporate the solvent and thermally process the resulting nano-sized particles. The investigation of optimum conditions for oxygen, argon, and air plasma ignition in the MPASD system was presented. Measured electron temperature of the plasma was between 6000K and 40000K for the plasma conditions used in the MPASD process. Successful deposition of Y2O3:Eu nano-particles using the MPASD system was achieved. MPASD process allows control of the particle's properties, shown through XRD and photoluminescence studies of the Y2O3:Eu coatings. The MPASD process settings effect on particles activated doping concentration and, as a result, its photoluminescence was shown.

This thesis describes the synthesis of yttrium oxide nanoparticles in an AOT/isooctane reverse micelle solution. Two synthetic methods are compared. First is the precipitation reaction between yttrium nitrate and ammonia, second is the hydrolysis of yttrium isopropoxide. The effects of annealing of the resulting the yttrium oxide nanoparticles are also described. The nitrate method produced network-like aggregates of yttrium oxide nanoparticles ranging from 10 nm to 40 nm in diameter. Reaction conditions, including the water/AOT ratio (1 to 15), the nitrate concentration (0.02 M to 1.0 M), the ammonia concentration (2 M to 14.8 M), the AOT concentration (0.1 M and 0.5 M), the aging time (1 h to 5 d), and the washing method, were varied to investigate their influence on nanoparticle formation. The optimized synthetic conditions were: a water/AOT ratio of 7.5, [NO₃⁻] = 0.5 M, [NH₃] = 2 M, and [AOT] = 0.1 M. The as-prepared yttrium oxide nanoparticles had highly distorted structures related to the cubic Y2O3 phase. Annealing improved the crystallinity of the as-prepared nanoparticle products and led to larger particles. As annealing temperatures increased, the yttrium oxide nanoparticles gradually evolved into the cubic Y₂O₃ phase. However, an unknown intermediate phase was also observed during the annealing process, which disappeared when the annealing temperature was sufficiently high and the annealing time was long enough (>1000 °C and 4 h). As-prepared products from the isopropoxide hydrolysis also contained network-like nanoparticle aggregates. Particle sizes ranged from 10 nm to 20 nm. Some experimental conditions were varied; they were the water/AOT ratio (10 to 40), the isopropoxide concentration (0.0001 M to 0.003 M), the aqueous phase pH (7.0 and 12.0), the aging temperature (room temperature, approximately 25 °C, and refluxing temperature, approximately, 100 °C), and the aging time (1 h to 5 d). Transmission Electronic Micrographs showed that products of desirable morphology could be produced in a much wider range of experimental conditions by this method compared to those produced by nitrate hydrolysis. / Master of Science

Esse trabalho de tese descreve a síntese e a caracterização de materiais amorfos e cristalinos na forma de pó e de filmes finos pertencentes ao sistema Er2O3-Y2O3-Al2O3-B2O3. O principal objetivo do trabalho foi o de obter filmes finos amorfos contendo íons Er3+ próximo à composição YAI3(BO3)4 (YAB), visando sua aplicação como amplificador em dispositivos ópticos integrados. Na síntese das amostras foi empregado o método dos precursores poliméricos e o método sol-gel. Uma vez estabelecida às condições de síntese das resinas e de sóis estáveis, diferentes parâmetros foram otimizados visando à deposição de filmes relativamente espessos e amorfos. As propriedades térmicas, estruturais e ópticas de amostras cristalinas ou amorfas, na forma de pó e na forma de filmes finos, foram caracterizadas através das técnicas de análise termogravimétrica, calorimetria exploratória diferencial, difração de raios X, espectroscopia vibracional na região do infravermelho com transformada de Fourier, espectroscopia Raman e microscopia eletrônica de varredura de alta resolução, microscopia de força atômica, espectroscopia \"m-line\", medidas de espectros de luminescência. Baseado na análise térmica e estrutural das amostras na forma de pó, foi possível realizar a síntese de amostras na forma de filmes finos de composição Y1-xErxAl3(BO3)4 que apresentaram características estruturais, microestruturais e ópticas adequadas à aplicação desejada. Através do estudo das propriedades térmicas e estruturais, foi observado que as amostras preparadas através do método dos precursores poliméricos e do método sol-gel apresentam respectivamente uma temperatura de transição vítrea (Tg) à 723 &#176C e à 746 &#176C e uma temperatura de cristalização (Tc) à 814 &#176C e à 830&#176C. O tratamento térmico à aproximadamente 1150 &#176C da amostra amorfa na forma de pó de composição Y0,9Er0,1Al3(BO3)4 contendo boro em excesso levou a obtenção de uma solução sólida cristalina de composição Y0,9Er0,1Al3(BO3)4. No que se refere às propriedades dos filmes finos, as melhores condições de densificação, homogeneidade, eficiência de guiamento, emissão luminescente e tempo de vida foram observadas quando os filmes de composição Y0,9Er0,1Al3(BO3)4 foram tratados entre as temperaturas de Tg e Tc. Os filmes amorfos de composição Y0,9Er0,1Al3(BO3)4 se comportam como guias monomodos, apresentando alta emissão luminescente e um tempo de vida comparável a outros sistemas amorfos a base de boro. Esse comportamento mostra a viabilidade de aplicação desses filmes amorfos como amplificadores ópticos planares. / This work specifies the synthesis and the characterization of amorphous and crystalline powder and thin films materials belonging to the Er2O3-Y2O3-Al2O3-B2O3 system. The main objective of this work was to develop amorphous thin film samples near the YAI3(BO3)4 composition with yttrium partially substituted by erbium Y1-xErxAl3(BO3)4 with the aim of applying these thin films as waveguide amplifiers in integrated optical systems. The polymeric precursor and the sol-gel methods were applied in order to produce such thin films. After the first step where the conditions to obtain very stable resins and sols was established, different parameters were adjusted aiming the deposition of thick and stable thin films. To well define the best conditions to obtain amorphous and dense thin films, the powder samples of the same compositions were first characterized by thermal analysis techniques, X-ray diffraction, IR and Raman spectroscopies, high resolution electron microscopy and atomic force microscopy. From thermal analysis and structural results, it was observed that the samples prepared from the polymeric precursor and sol-gel methods exhibit glass transition temperatures, Tg, at 723 and 746 &#176C and cristallisation temperatures, Tc, at 814 and 830 &#176C, respectively. The heat treatment at around 1150 &#176C of Y0,9Er0,1Al3(BO3)44 powder sample containing a smaller amount of boron in excess produced by both methods lead to the formation of a crystalline solid solution of the same composition without the presence of secondary phases. These results show that dense, free of cracks, thick and homogeneous thin films could be obtained when they were submitted at a heat treatment in temperatures between Tg and Tc. From the \"m-line\" spectroscopy technique and luminescence measurements we observed that the Y0,9Er0,1Al3(BO3)4 amorphous thin films can be considered as monomode waveguides showing a high luminescence intensities and a lifetime similar to other amorphous borate systems. These results show the potentiality to apply such amorphous thin films as optical planar amplifiers.

Le phénomène d’up-conversion de photon (UpC) permet de générer de la lumière à longueurs d’onde plus courtes que la longueur d’onde d’excitation. Dans cette recherche, la synthese de couches minces dopées avec des ions de terres rares (RE3+) optiquement actifs, leurs caractérisations structurales, ainsi que leurs propriétés optiques et de photoluminescentes ont été étudiées. Les couches ont été élaborées par deux voies de dépôt de couche sur du silicium et des substrats transparents: tout d’abord, un dépôt chimique organométallique en phase vapeur (LI-MOCVD, AA-MOCVD) est utilisé pour le dépôt des couches minces de YF3 et Y2O3 co-dopées Er/Yb. Il est démontré que l’émission d’UpC de Er3+ avec une excitation à 972 nm est influencée par le réseau hôte. Par ailleurs, le traitement sol-gel, une technique chimique par voie humide, est utilisé pour la fabrication de couches minces Y2O3, SiO2 et TiO2 co-dopées Er/Yb par spin-coating. Une optimisation de l’´emission de lumière par UpC a été atteinte grâce à l’ajustement de la concentration de RE et de la température de traitement thermique. De plus, une approche différente a été étudiée pour atteindre une émission UpC renforcée : l’utilisation de microcavités diélectriques de Fabry-Pérot obtenues par sol-gel, constitués d’un empilement de couches de silice et d’oxyde de titane, avec Er/Yb:Y2O3 comme couche de cavité. Le but de ce travail est de répondre aux questions suivantes: comment la nature du réseau hôte et le niveau de dopage influencent l’émission radiative de l’Er3+? Quelles sont les conditions pour un bon matériau d’UpC et ses limites? Nous incluons également une discussion sur les perspectives d’une application possible d’une couche d’UpC dans un dispositif de cellule solaire, qui pourrait améliorer la réponse dans l’infrarouge. / Photon up-conversion (UpC) allows the generation of light of shorter wavelengths compared to the excitation wavelength. In this work the synthesis of thin films doped with optically active rare earth (RE3+) ions, their structural characterization, as well the optical and photoluminescence properties are highlighted. The emphasis lies on two different routes of film deposition on silicon and transparent substrates: first, metalorganic chemical vapor deposition (LI-MOCVD, AA-MOCVD) is introduced for the deposition of Er/Yb-doped YF3 and Y2O3 films and it is demonstrated, how the UpC emission of Er3+ upon 972 nm excitation is influenced by the host lattice. Secondly, sol-gel processing, a wet-chemical technique, is used for the fabrication of Er/Yb-doped Y2O3, SiO2 and TiO2 thin films by spin-coating. Optimization of the up-converted light emission was achieved through adjusting the RE concentration and the processing temperature. Moreover, in a different approach for achieving an enhanced UpC emission, sol-gel derived Fabry-Pérot dielectric microcavities, consisting of a multilayer stack of silica and titania layers and Er/Yb: Y2O3 as the cavity layer, are investigated. The aim of this work is to address the questions, how does the nature of the host lattice and doping level influence the radiative emission in Er3+, what are the requirements for a good upconverter material and what are the limitations? We also include a discussion of the application of an upconverter to a solar cell device, which may debatably enhance the response in the infrared.

Esse trabalho de tese descreve a síntese e a caracterização de materiais amorfos e cristalinos na forma de pó e de filmes finos pertencentes ao sistema Er2O3-Y2O3-Al2O3-B2O3. O principal objetivo do trabalho foi o de obter filmes finos amorfos contendo íons Er3+ próximo à composição YAI3(BO3)4 (YAB), visando sua aplicação como amplificador em dispositivos ópticos integrados. Na síntese das amostras foi empregado o método dos precursores poliméricos e o método sol-gel. Uma vez estabelecida às condições de síntese das resinas e de sóis estáveis, diferentes parâmetros foram otimizados visando à deposição de filmes relativamente espessos e amorfos. As propriedades térmicas, estruturais e ópticas de amostras cristalinas ou amorfas, na forma de pó e na forma de filmes finos, foram caracterizadas através das técnicas de análise termogravimétrica, calorimetria exploratória diferencial, difração de raios X, espectroscopia vibracional na região do infravermelho com transformada de Fourier, espectroscopia Raman e microscopia eletrônica de varredura de alta resolução, microscopia de força atômica, espectroscopia \"m-line\", medidas de espectros de luminescência. Baseado na análise térmica e estrutural das amostras na forma de pó, foi possível realizar a síntese de amostras na forma de filmes finos de composição Y1-xErxAl3(BO3)4 que apresentaram características estruturais, microestruturais e ópticas adequadas à aplicação desejada. Através do estudo das propriedades térmicas e estruturais, foi observado que as amostras preparadas através do método dos precursores poliméricos e do método sol-gel apresentam respectivamente uma temperatura de transição vítrea (Tg) à 723 &#176C e à 746 &#176C e uma temperatura de cristalização (Tc) à 814 &#176C e à 830&#176C. O tratamento térmico à aproximadamente 1150 &#176C da amostra amorfa na forma de pó de composição Y0,9Er0,1Al3(BO3)4 contendo boro em excesso levou a obtenção de uma solução sólida cristalina de composição Y0,9Er0,1Al3(BO3)4. No que se refere às propriedades dos filmes finos, as melhores condições de densificação, homogeneidade, eficiência de guiamento, emissão luminescente e tempo de vida foram observadas quando os filmes de composição Y0,9Er0,1Al3(BO3)4 foram tratados entre as temperaturas de Tg e Tc. Os filmes amorfos de composição Y0,9Er0,1Al3(BO3)4 se comportam como guias monomodos, apresentando alta emissão luminescente e um tempo de vida comparável a outros sistemas amorfos a base de boro. Esse comportamento mostra a viabilidade de aplicação desses filmes amorfos como amplificadores ópticos planares. / This work specifies the synthesis and the characterization of amorphous and crystalline powder and thin films materials belonging to the Er2O3-Y2O3-Al2O3-B2O3 system. The main objective of this work was to develop amorphous thin film samples near the YAI3(BO3)4 composition with yttrium partially substituted by erbium Y1-xErxAl3(BO3)4 with the aim of applying these thin films as waveguide amplifiers in integrated optical systems. The polymeric precursor and the sol-gel methods were applied in order to produce such thin films. After the first step where the conditions to obtain very stable resins and sols was established, different parameters were adjusted aiming the deposition of thick and stable thin films. To well define the best conditions to obtain amorphous and dense thin films, the powder samples of the same compositions were first characterized by thermal analysis techniques, X-ray diffraction, IR and Raman spectroscopies, high resolution electron microscopy and atomic force microscopy. From thermal analysis and structural results, it was observed that the samples prepared from the polymeric precursor and sol-gel methods exhibit glass transition temperatures, Tg, at 723 and 746 &#176C and cristallisation temperatures, Tc, at 814 and 830 &#176C, respectively. The heat treatment at around 1150 &#176C of Y0,9Er0,1Al3(BO3)44 powder sample containing a smaller amount of boron in excess produced by both methods lead to the formation of a crystalline solid solution of the same composition without the presence of secondary phases. These results show that dense, free of cracks, thick and homogeneous thin films could be obtained when they were submitted at a heat treatment in temperatures between Tg and Tc. From the \"m-line\" spectroscopy technique and luminescence measurements we observed that the Y0,9Er0,1Al3(BO3)4 amorphous thin films can be considered as monomode waveguides showing a high luminescence intensities and a lifetime similar to other amorphous borate systems. These results show the potentiality to apply such amorphous thin films as optical planar amplifiers.

In the present dissertation the formation of microstructure, the kinetics of densification and the formation of surface layers developing during liquid phase sintering of silicon carbide are studied. The focus is on the additive systems Al2O3 plus Y2O3 and AlN plus Y2O3. Phase and especially liquid phase formation in both of the systems SiC, Al2O3 , Y2O3 and AlN, Al2O3 , Y2O3 are investigated in detail examining 12 espectively 17 different compositions per system. Melting temperatures have been determined by TG/DTA, in both systems for the first time. Phase composition of samples was analysed by the combination of XRD, SEM and EDX. In the system SiC, Al2O3 , Y2O3 the formation of the phases expected from the quasibinary Al2O3 , Y2O3 could be observed thus silicon carbide has to be in equilibrium with the oxide additives. The low solubility of SiC in the oxide melt, which was suggested by Hoffmann and Nader, could be confirmed. In the system AlN, Al2O3 , Y2O3 the formation of phases as stated by Medraj was confirmed, except for the dimension of the stability region of the γ- spinel and YAG which is wider in the present work. For the first time diffusion coefficients of the species Y3+ and Al3+ in the oxide melt formed by Al2O3 and Y2O3 at temperatures above 1825 ◦ C were determined. The values are in the order of 2 · 10−6 cm2 /s which results in a diffusion length of 14.1 μm for a diffusion time of one second. This allows the fast equilibration of Y and Al deficiencies. Kinetics of densification was modeled by kinetic field, master curve and thermokinetic method, based on detailed experimental investigation of the shrinkage during liquid phase sintering of SiC. It could be proved that the first 30 − 40 % of densification are controlled by solid phase reactions which accelerate particle rearrangement without presence of a liquid phase. During the remaining 60 − 70 % of densification a liquid is present, resulting in the predominance of mechanisms of liquid phase sintering. The models deliver activation energies in the range from 608 KJ/mol to 1668 kJ/mol and allow, within the scope of validity of each method the prediction of densification during liquid phase sintering of silicon carbide. When sintering silicon carbide with Al2O3 plus Y2O3 the formation of several surface layers, depending on atmosphere, maximum temperature, dwelling time and amount and composition of additives was observed. In nitrogen atmosphere with low partial pressures a surface layer consisting of AlN is forming whilst at high partial pressures SiAlON- polytypes occur. After sintering in Argon or Ar-CO- atmosphere three main types of surface layers are present. One consists of alumina, one contains only YAG and one shows highly porous, additive depleted regions. An explanation for the formation of the several surface layers could be given by the combination of the determined diffusion coefficients with the results achieved in the thermodynamics part. The results achieved in this work can be a contribution to the knowledge based design of the production process of liquid phase sintering of silicon carbide.

L'objectif de ce travail est d'étudier un matériau up-converteur sous différentes formes afin de pourvoir l'appliquer au photovoltaïque (cellules de 3ième génération). L'oxyde d'yttrium possédant des propriétés particulièrement intéressantes pour l'up-conversion (gap et indice de réfraction élevés, faible énergie de phonons, dopage facile) a été choisi comme matériau up-converteur et a permis d'étudier les propriétés d'up-conversion de ce matériau sous formes de particules sphériques monodisperses et sous forme de couches minces. Les ions erbium et ytterbium, étant connus pour leurs très bonnes propriétés en up-conversion, ont été choisis comme dopants. Deux méthodes de synthèses : la synthèse par précipitation homogène et la synthèse par voie hydrothermale, ont permis d'obtenir les particules respectant les contraintes morphologiques prédéfinies. L'étude de ce matériau sous forme de particules a permis de déterminer l'influence des différents paramètres physiques et chimiques sur les propriétés d'up-conversion. Les couches minces d'oxyde d'yttrium ont été obtenues par spin-coating. L'étude de ces couches minces a permis de démontrer que les rendements de luminescence mesurés sur les couches sont beaucoup plus faibles que ceux des particules; cependant, la nanostructuration des couches minces a permis de démontrer une exaltation des propriétés de luminescence grâce à l'interaction des ions émetteurs avec les structures plasmoniques résonantes. Des études réalisées en vue de l'application de l'up-conversion au photovoltaïque (génération de courant dans une cellule bifaciale c-Si par excitation sub-band-gap, mesure en fonction de la température, up-conversion sous excitation solaire) ont démontré la faisabilité du concept et a permis de conclure que la réalisation du concept up-conversion/photovoltaïque doit encore passer par l'optimisation des matériaux up-converteur.