The influence of photon excitation and proton irradiation on the luminescence properties of yttria stabilized zirconia doped with praseodymium ions

Lanthanide doped zirconia based materials are promising phosphors for lighting applications. Transparent yttria stabilized zirconia fibres, in situ doped with Pr3+ ions, were grown by the laser floating zone method. The single crystalline doped fibres were found to be homogeneous in composition and provide an intense red luminescence at room temperature. The stability of this luminescence due to transitions between the 1D2 → 3H4 multiplets of the Pr3+ ions (intra-4f2 configuration) was studied by photo- and iono-luminescence. The evolution of the red integrated photoluminescence intensity with temperature indicates that the overall luminescence decreases to ca. 40% of the initial intensity at 14 K when heated to room temperature (RT). RT analysis of the iono-luminescence dependence on irradiation fluence reveals a decrease of the intensity (to slightly more than ∼60% of the initial intensity after 25 min of proton irradiation exposure). Nevertheless the luminescence intensity saturates at non-zero values for higher irradiation fluences revealing good potential for the use of this material in radiation environments.

Preparação e caracterização de fibras e nanotubos de BiFeO3 e FeNbO4

Esta dissertação teve como objetivo a produção e caracterização física de fibras e nanotubos de BiFeO3 e FeNbO4. Para o desenvolvimento destes materiais utilizou-se a técnica de fusão com laser (LFZ), o método sol-gel (Pechini) e o método de poros absorventes. As amostras obtidas foram sujeitas a uma caracterização estrutural por difração de raios-X e espetroscopia de Raman, morfológica por microscopia electrónica de varrimento e elétrica por medidas de constante dielétrica. Os resultados obtidos com a técnica de difração de raios-X mostraram que o gel com tratamento a 750 ºC é polifásico. Para conseguir produzir nanotubos escolheu-se o LaCoO3 como material alternativo. Usando a técnica de fusão de zona com laser (LFZ) obtiveram-se fibras de BiFeO3, FeNbO4 e compósitos de BiFeO3+FeNbO4. Com esta técnica foram crescidas fibras a várias velocidades (5, 10, 25, 50, 100 e 200 mm/h), tendo os resultados obtidos com a difração de raios-X evidenciado que todas as amostras obtidas são polifásicas, sendo a amostra de 10 mm/h para o BiFeO3 e a de 5 mm/h para o FeNbO4 as que apresentam melhores propriedades. As amostras de 5 mm/h de todos os compósitos são aquelas que possuem menor quantidade de segundas fases e portanto foram alvo de estudo mais aprofundado. A caracterização dielétrica permitiu verificar que todas as amostras apresentam fenómenos de relaxação dielétrica. Verifica-se também que para o BiFeO3 a constante dielétrica é superior na amostra crescida à velocidade de 10 mm/h, para o FeNbO4 é superior na amostra crescida a 5 mm/h e nos compósitos a amostra com 75% de BiFeO3 e 25% de FeNbO4 apresenta um comportamento diferente das restantes, eventualmente devido à sua microestrutura singular.

Development of Zirconia based phosphors for application in lighting and as luminescent bioprobes

The strong progress evidenced in photonic and optoelectronic areas, accompanied by an exponential development in the nanoscience and nanotechnology, gave rise to an increasing demand for efficient luminescent materials with more and more exigent characteristics. In this field, wide band gap hosts doped with lanthanide ions represent a class of luminescent materials with a strong technological importance. Within wide band gap material, zirconia owns a combination of physical and chemical properties that potentiate it as an excellent host for the aforementioned ions, envisaging its use in different areas, including in lighting and optical sensors applications, such as pressure sensors and biosensors. Following the demand for outstanding luminescent materials, there is also a request for fast, economic and an easy scale-up process for their production. Regarding these demands, laser floating zone, solution combustion synthesis and pulsed laser ablation in liquid techniques are explored in this thesis for the production of single crystals, nanopowders and nanoparticles of lanthanides doped zirconia based hosts. Simultaneously, a detailed study of the morphological, structural and optical properties of the produced materials is made. The luminescent characteristics of zirconia and yttria stabilized zirconia (YSZ) doped with different lanthanide ions (Ce3+ (4f1), Pr3+ (4f2), Sm3+ (4f5), Eu3+ (4f6), Tb3+ (4f8), Dy3+ (4f9), Er3+ (4f11), Tm3+ (4f12), Yb3+ (4f13)) and co-doped with Er3+,Yb3+ and Tm3+,Yb3+ are analysed. Besides the Stokes luminescence, the anti- Stokes emission upon infrared excitation (upconversion and black body radiation) is also analysed and discussed. The comparison of the luminescence characteristics in materials with different dimensions allowed to analyse the effect of size in the luminescent properties of the dopant lanthanide ions. The potentialities of application of the produced luminescent materials in solid state light, biosensors and pressure sensors are explored taking into account their studied characteristics.