CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / CNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológico / FAPEMIG - Fundação de Amparo a Pesquisa do Estado de Minas Gerais / A caracterização de materiais vítreos dopados tem sido uma área importante para o desenvolvimento de tecnologias fotônicas. Porém, com o desenvolvimento da nanociência e a descoberta das propriedades quânticas dos nanocristais, a quantidade de materiais vítreos a serem estudados aumentou de forma abrupta, o qual despertou um forte interesse da comunidade científica visando possíveis aplicações tecnológicas. O presente trabalho tem como objetivo investigar o índice de refração não linear da matriz vítrea a base de fosfato (P2O5 + AhO3 + Na2O + K2O) dopada com íons de neodímio e nanocristais de CdS. Destaca-se que a pesquisa corresponde à caracterização de uma matriz fosfata pouco conhecida na literatura, com dopantes de categorias distintas, sendo um Terra Rara e um nanocristal, nos quais apresentam picos de absorção próximos. Para a presente caracterização não linear, foi utilizada a técnica de Z-Scan, conhecido na literatura por sua simplicidade e precisão quando comparada com outras técnicas capazes de realizar a mesma medida. Medidas de absorção ótica e tempo de vida também foram feitas, pois fornecem parâmetros lineares para o cálculo das propriedades não lineares. Os resultados mostram que existe uma interação entre os dopantes, capaz de gerar uma variação nos parâmetros lineares e não lineares em estudo. / The characterization of doped glasses has been an important area for the development of photonic technologies. However, the development of nanoscience and the discovery of the quantic properties of nanocrystals, increased the number of researches in glass materials with interest in technological applications by the scientific community. This work aims to investigate the nonlinear refractive index of the phosphate glass matrix (P2O5 + Al2O3 + Na2O + K2O) doped with neodymium ions and CdS nanocrystals. This research characterizes a phosphate glass matrix, which is not well known in the literature with different dopants, in this case, rare earths and nanocrystals, which they show similar absorption peaks at ultraviolet. For a nonlinear optics characterization was used the Z-Scan technique, known to its simplicity and precision when compared to other techniques. Linear optical measurements were also made, such as optical absorption and lifetime, to calculate of non-linear optics properties. The results show there is an interaction between the dopants, capable of generating a variation in linear and nonlinear optical parameters under study. / Dissertação (Mestrado)

Orientadores: Ítalo Odone Mazali, Fernando Aparecido Sigoli / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-22T16:11:21Z (GMT). No. of bitstreams: 1 Mello_LauraBissolide_M.pdf: 5917459 bytes, checksum: 84ba21daf327140c83f0038b51e81366 (MD5) Previous issue date: 2013 / Resumo: No presente trabalho, buscou-se avaliar as mudanças promovidas pela substituição parcial e total de TiO2 por GeO2 em vidros niobofosfato co-dopados com Er/Yb previamente estudados pelo grupo. Uma série de sistemas vítreos de composições 20Na2O-30Nb2O5-(5-y-z)Al2O3-30P2O5-(15-x)TiO2-xGeO2-yEr2O3-zYb2O3 com x = (0; 5; 10; 15), y = (0; 1), z = (0; 2) mol%, obtidos por fusão-resfriamento, foram investigados quanto à sua estrutura, propriedades ópticas e de luminescência. Análises de FTIR e Raman sugerem que a estrutura de vidro não se altera de forma significativa ao longo da série de substituições de TiO2 por GeO2 e, consequentemente, a coordenação dos elementos devem se manter semelhantes. Na literatura reporta-se que íons Ge têm preferencialmente coordenação 4; entretanto, nos sistemas estudados, sugere-se que o Ge apresente coordenação 6, semelhante à do Ti substituído. Esta proposição é confirmada pelos espectros de P MAS-NMR, os quais indicam que os vidros possuem cadeias majoritariamente do tipo pirofosfato, sem mudança no grau de polimerização com as substituições. Também pôde-se confirmar a manutenção da coordenação com os resultados obtidos da fotoluminescência dos sistemas vítreos co-dopados, nos quais os tempos de vida de emissão do íon Er (5 ms) e parâmetros de intensidade de Judd-Ofelt dos diferentes sistemas vítreos são muito semelhantes entre si, e o processo de emissão de upconversion dos vidros dopados envolve 1,5 fótons. Quanto ao comportamento térmico, observa-se que os vidros contendo maior proporção de GeO2 têm maior estabilidade térmica e são, portanto, mais resistentes à desvitrificação quando comparado às composições contendo mais TiO2 / Abstract: The aim of this work was to study the changes promoted by partial and complete substitution of TiO2 by GeO2 in Er/Yb co-doped niobophosphate glasses previously studied by the group. A series of glasses with composition 20Na2O-30Nb2O5-(5-y-z)Al2O3-30P2O5-(15-x)TiO2-xGeO2-yEr2O3-zYb2O3 with x = (0; 5; 10; 15), y = (0; 1), z = (0; 2) mol%, prepared by quenching-melt process, were investigated with respect to their structural, optical and luminescence properties. FTIR and Raman analysis suggest that the glassy chains didn¿t suffer relevant modifications with the TiO2 substitutions by GeO2 and as a consequence, the coordination of the ions weren¿t affected. The coordination of the Ge ion is reported as mainly thetraedral; however, in the present work, is suggested that Ge ion has an octahedral coordination, as well the TiO2 substituted. This proposition is confirmed by the P MAS-NMR spectra, which showed mainly pyrophosphate chains of the different glasses, without changings in their polymerization after the substitutions. The similar ions coordination was also confirmed by the photoluminescence behavior of the different co-doped samples, which showed equal Er emission decay lifetimes (5 ms) and Judd-Ofelt intensity parameters, and the upconversion emission process involved 1,5 photons. Regarding the thermal behavior, it is noted that the glasses containing higher proportions of GeO2 have higher thermal stability and are therefore more resistant to devitrification when compared to compositions containing more TiO2 / Mestrado / Quimica Inorganica / Mestra em Química

Les besoins de nouvelles technologies en télécommunications motivent la recherche de matériaux participant à la formation de composants optiques. Dans ce but, l’étude de la photostructuration de nouvelles formulations de verres possédant des propriétés optiques ajustables a été réalisée. Deux cas ont été étudiés : la modification du réseau vitreux ou l’introduction d’ions photosensibles au sein du verre. - Des verres oxysulfures de germanium et de gallium ont été élaborés sous forme de massif, et sous forme de couche mince. Leurs propriétés optiques sont intermédiaires à celles des composés purs Ge(Ga)O2 et Ge(Ga)S2. La photosensibilité des verres diminue avec l’augmentation de la valeur du rapport O/S des matériaux. - L’ajout d’ions argent au sein de verres phosphates de zinc a été étudié. Plusieurs techniques de réduction de l’ion argent dans ces verres ont été explorées comme l’irradiation par faisceau électronique, par rayonnement gamma ou par Laser. Dans le cas particulier d’une irradiation par laser femtoseconde de cadence de 8 Mhz et émettant à 1030 nm, il a été possible de créer des structures optiques de 85 nm environ, donc bien inférieur à la longueur d’onde utilisée pour l’écriture. Ces premiers résultats offrent une nouvelle alternative à la création dans le futur de structures photoniques composites. / The increment of the need of new technologies in photonics is a perfect vector for the research and development of new components for integrated optics. The photostructuration of new glassy materials with novel optical properties is proposed. Two approaches have been conducted : Modification of the glass matrix or addition of photosensitive ions. - Germanium and gallium oxysulfide glasses have been elaborated into bulk glasses as well as amorphous thin films. They exhibit optical properties in between their respective pure sulphide or oxide counterpart in the Ge(Ga)O2 - Ge(Ga)S2 system. The photosensitivity of the oxysulfide glasses lowers as the oxygen/sulphur ratio of the glasses is increased. - The photosensitivity of silver ions within silver phosphate glasses was studied as well. Several techniques were used in order to trigger the reduction of silver such as gamma ray or electron beam irradiation, or laser beam exposure. Under a femtosecond laser with a repetition rate of 8 Mhz, emitting at 1030 nm, it was possible to create optical objects, below the diffraction limit, of about 85 nm. Those results are a new alternative for the creation of photonic composite structures.

This thesis concerns the development of a new series of Sr-doped phosphate-based glasses for biomedical applications. Such glasses in powder form are envisaged to have applications in novel composite restorations where the following is achievable: dentin cell-mediated bioremineralization, dental pulp regeneration and as carrier for therapeutics or antibacterial ions.The initial aim was to produce soluble porous phosphate glasses using the sol-gel method (phosphate-alkoxide based sol-gel process). Knowing the effect that the variation of Ca content has on the dissolution properties of the glass, a series of glasses where Ca was progressively increased at the expense of Na was produced. The structure of the prepared samples was probed by XRD, XRF and FTIR to confirm the successful synthesis of the target phosphate-based glass compositions. After that a promising methodology was established, attempts were made to replace Ca with Sr. Different Sr sources were used without success due to the difficulty to fully dissolve those precursors in the sol-gel mixture. Subsequently, the issue of the toxicity of some precursors and solvents used in the sol-gel procedure was recognised. To overcome this obstacle, efforts were made to replace the toxic precursor chemicals with safer ones. Nevertheless, due to the low solubility of some new precursors and the low reactivity of others, the sol-gel process did not proceed in a predictable and reproducible fashion. At this stage, the sol-gel route was put aside, and two alternative soft and water-based chemical approaches were experimented: the precipitation method and the coacervation process. The first one was found to be unsuitable for our needs for two main reasons: 1) the presence of Na in the composition generated a crystalline material (instead of a glassy amorphous one); 2) the Ca/P ratio of our composition fell in the range of crystalline phase by using this method. In addition, the yield was really low. The second method (coacervation process) was a complete success. The glassy nature of the materials obtained was proved by XRD and XRF and the surface features were tested by BET and SEM. The process was retained for a while as the preferred synthesis route and both the scale-up effect and the possibility to add Sr were analysed. The production scale of the material was increased by 5 times and different Sr sources were tested to find the best one. XRD and XRF analysis proved both the success of the scale-up and the incorporation of the Sr in glass composition / This thesis concerns the development of a new series of Sr-doped phosphate-based glasses for biomedical applications. Such glasses in powder form are envisaged to have applications in novel composite restorations where the following is achievable: dentin cell-mediated bioremineralization, dental pulp regeneration and as carrier for therapeutics or antibacterial ions.The initial aim was to produce soluble porous phosphate glasses using the sol-gel method (phosphate-alkoxide based sol-gel process). Knowing the effect that the variation of Ca content has on the dissolution properties of the glass, a series of glasses where Ca was progressively increased at the expense of Na was produced. The structure of the prepared samples was probed by XRD, XRF and FTIR to confirm the successful synthesis of the target phosphate-based glass compositions. After that a promising methodology was established, attempts were made to replace Ca with Sr. Different Sr sources were used without success due to the difficulty to fully dissolve those precursors in the sol-gel mixture. Subsequently, the issue of the toxicity of some precursors and solvents used in the sol-gel procedure was recognised. To overcome this obstacle, efforts were made to replace the toxic precursor chemicals with safer ones. Nevertheless, due to the low solubility of some new precursors and the low reactivity of others, the sol-gel process did not proceed in a predictable and reproducible fashion. At this stage, the sol-gel route was put aside, and two alternative soft and water-based chemical approaches were experimented: the precipitation method and the coacervation process. The first one was found to be unsuitable for our needs for two main reasons: 1) the presence of Na in the composition generated a crystalline material (instead of a glassy amorphous one); 2) the Ca/P ratio of our composition fell in the range of crystalline phase by using this method. In addition, the yield was really low. The second method (coacervation process) was a complete success. The glassy nature of the materials obtained was proved by XRD and XRF and the surface features were tested by BET and SEM. The process was retained for a while as the preferred synthesis route and both the scale-up effect and the possibility to add Sr were analysed. The production scale of the material was increased by 5 times and different Sr sources were tested to find the best one. XRD and XRF analysis proved both the success of the scale-up and the incorporation of the Sr in glass composition

La focalisation de lasers à impulsions ultra-brèves dans les verres a montré des potentialités importantes pour la structuration des matériaux transparents, permettant d’envisager la réalisation de dispositifs tout-optique en une seule étape. Le développement de nouveaux matériaux vitreux de composition 40P2O5-55ZnO-xAg2O-(5-x)Ga2O3 permet de tirer avantage de la photosensibilité de l’ion Ag+ pour la structuration de propriétés optiques au cœur du matériau. L’augmentation du taux d’oxyde de gallium provoque la dépolymérisation des chaînes phosphates et s’accompagne de la réticulation du réseau vitreux par des polyèdres GaOx (4 ≤ x ≤ 6). La formation de des derniers n’affecte pas les propriétés d’émission lumineuses, qui proviennent des ions Ag+ isolés dans différents sites cristallographiques. L’exposition des verres sous faisceau laser intense provoque la formation de centres-trous Ag2+, responsables d’une luminescence intense, et de pièges d'électrons Ag0. Un traitement thermique consécutif ou simultané à l’irradiation provoque la dissociation de ces espèces, et s’accompagne de la formation d’agrégats moléculaires de la forme Agmx+. L’utilisation d’un laser femtoseconde à haute cadence permet, en combinant création de paires électron-trou et élévation locale de la température, de réaliser des architectures complexes conduisant à la structuration de propriétés optiques. / The development of new vitreous materials in the 40P2O5-55ZnO-xAg2O-(5-x)Ga2O3 diagram permits to take advantage of the Ag+ ion photosensitivity for structuring optical properties within the material. Increasing the gallium oxide content leads to the depolymerisation of the phosphate chains and the reticulation of the glass network by GaOx polyhedra (4 ≤ x ≤ 6). The formation of the latters does not affect the luminescence properties which are related to silver ions in various crystallographic environments. The intense laser exposure of the glasses leads to the formation of Ag2+ hole centers responsible for an intense luminescence and electron traps Ag0. A subsequent or simultaneous heat treatment provokes the dissociation of the hole centers and is accompanied by the formation of Agmx+ molecular-like clusters. The use of a high repetition rate femtosecond laser combining electrons and hole traps and temperature rising permits to obtain complex features leading to the structuring of optical properties.

SANTOS, Clenilton Costa dos. Propriedades ópticas dos vidros Er3+:PbPO4. 2010. 96 f. Tese (Doutorado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2010. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2014-11-03T18:38:41Z No. of bitstreams: 1 2010_tese_ccsantos.pdf: 4778732 bytes, checksum: e9324ded793c2e668aa603d0ce9ecc71 (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2014-11-03T19:51:31Z (GMT) No. of bitstreams: 1 2010_tese_ccsantos.pdf: 4778732 bytes, checksum: e9324ded793c2e668aa603d0ce9ecc71 (MD5) / Made available in DSpace on 2014-11-03T19:51:31Z (GMT). No. of bitstreams: 1 2010_tese_ccsantos.pdf: 4778732 bytes, checksum: e9324ded793c2e668aa603d0ce9ecc71 (MD5) Previous issue date: 2010 / In this work we employ several techniques to investigate the optical properties of moderately high Er3+-doped lead phosphate (EDLP) glasses. The third-order optical susceptibility, χ3, and dispersion of the linear refractive index, n0(λ), of Er3+:PbPO4 were measured in the wavelength range between 400 and 1940 nm by using the spectrally resolved femtosecond Maker fringes technique. The nonlinear refractive index, n2, obtained from the third-order susceptibility was found to be five times higher than that of silica. For comparison purposes, the Z-scan technique was also employed to obtain the values of n2 of EDLP at several wavelengths, and the values obtained using the two techniques agree to within 15%. From the data obtained by absorption measurements, the Judd-Ofelt theory was employed to calculate the intensity-dependent parameters Ωλ (λ = 2, 4, and 6). We observed that increasing Er3+ content, Ω4 and Ω6 remain constant, while Ω2 decreases. Green, red, and infrared emissions centered at 530, 550, 660, and 1530 nm were observed under excitation at 800 nm. The lifetime of the Er3+: 4I13/2 → 4I15/2 (1530 nm) transition decreases with increasing Er3+ content, reflecting how significant the non-radiative process associated with this transition is. The McCumber theory was used to calculate, from absorption cross-section, the stimulated emission cross-section of the Er3+: 4I13/2 → 4I15/2 transition. A strong re-absorption of the fluorescence at 1530 nm was also observed and analyzed. Finally, we discuss the potential use of Er3+:PbPO4 glasses in photonics devices. / Neste trabalho utilizamos várias técnicas para investigar as propriedades ópticas dos vidros fosfato de chumbo (PbPO4) com concentrações moderadamente altas de íons de érbio (Er3+), EDLP. Medimos a susceptibilidade de terceira ordem, χ3, e a dispersão do índice de refração linear, n0(λ), dos vidros EDLP na região de comprimento de onda entre 400 e 1940 nm, por meio da técnica de Franjas de Maker. A partir do valor de χ3, calculamos o índice de refração não-linear, n2, cujo valor é cerca de cinco vezes maior que o da sílica (SiO2). Também obtivemos os valores de n2 dos vidros EDLP, através da técnica de varredura Z para vários comprimentos de onda. A diferença entre os valores obtidos pelas duas técnicas foi de 15%. Realizamos medidas de absorção óptica, cujos dados foram utilizados para calcular os parâmetros fenomenológicos Ωλ da teoria de Judd-Ofelt. Observamos que Ω4 e Ω6 permanecem praticamente constante com o aumento da concentração de Er3+, ao passo que Ω2 diminui. Excitando as amostras em 800 nm foi possível verificar emissões no verde, vermelho e infravermelho, centradas em 530, 550, 660 e 1530 nm, respectivamente. O tempo de vida da transição 4I13/2 → 4I15/2 (em 1530 nm) do Er3+ diminui com o aumento da concentração de Er3+, refletindo o quão importante é o processo não-radiativo associado a esta transição. A teoria de McCumber foi usada para calcular, a partir da seção de choque de absorção, a seção de choque da emissão estimulada da transição 4I13/2 → 4I15/2 do Er3+. Observamos e analisamos uma forte reabsorção da fluorescência em 1530 nm. Finalmente, discutimos a aplicabilidade dos vidros EDLP em dispositivos fotônicos.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Neste trabalho utilizamos vÃrias tÃcnicas para investigar as propriedades Ãpticas dos vidros fosfato de chumbo (PbPO4) com concentraÃÃes moderadamente altas de Ãons de Ãrbio (Er3+), EDLP. Medimos a susceptibilidade de terceira ordem, χ3, e a dispersÃo do Ãndice de refraÃÃo linear, n0(λ), dos vidros EDLP na regiÃo de comprimento de onda entre 400 e 1940 nm, por meio da tÃcnica de Franjas de Maker. A partir do valor de χ3, calculamos o Ãndice de refraÃÃo nÃo-linear, n2, cujo valor à cerca de cinco vezes maior que o da sÃlica (SiO2). TambÃm obtivemos os valores de n2 dos vidros EDLP, atravÃs da tÃcnica de varredura Z para vÃrios comprimentos de onda. A diferenÃa entre os valores obtidos pelas duas tÃcnicas foi de 15%. Realizamos medidas de absorÃÃo Ãptica, cujos dados foram utilizados para calcular os parÃmetros fenomenolÃgicos Ωλ da teoria de Judd-Ofelt. Observamos que Ω4 e Ω6 permanecem praticamente constante com o aumento da concentraÃÃo de Er3+, ao passo que Ω2 diminui. Excitando as amostras em 800 nm foi possÃvel verificar emissÃes no verde, vermelho e infravermelho, centradas em 530, 550, 660 e 1530 nm, respectivamente. O tempo de vida da transiÃÃo 4I13/2 → 4I15/2 (em 1530 nm) do Er3+ diminui com o aumento da concentraÃÃo de Er3+, refletindo o quÃo importante à o processo nÃo-radiativo associado a esta transiÃÃo. A teoria de McCumber foi usada para calcular, a partir da seÃÃo de choque de absorÃÃo, a seÃÃo de choque da emissÃo estimulada da transiÃÃo 4I13/2 → 4I15/2 do Er3+. Observamos e analisamos uma forte reabsorÃÃo da fluorescÃncia em 1530 nm. Finalmente, discutimos a aplicabilidade dos vidros EDLP em dispositivos fotÃnicos. / In this work we employ several techniques to investigate the optical properties of moderately high Er3+-doped lead phosphate (EDLP) glasses. The third-order optical susceptibility, χ3, and dispersion of the linear refractive index, n0(λ), of Er3+:PbPO4 were measured in the wavelength range between 400 and 1940 nm by using the spectrally resolved femtosecond Maker fringes technique. The nonlinear refractive index, n2, obtained from the third-order susceptibility was found to be five times higher than that of silica. For comparison purposes, the Z-scan technique was also employed to obtain the values of n2 of EDLP at several wavelengths, and the values obtained using the two techniques agree to within 15%. From the data obtained by absorption measurements, the Judd-Ofelt theory was employed to calculate the intensity-dependent parameters Ωλ (λ = 2, 4, and 6). We observed that increasing Er3+ content, Ω4 and Ω6 remain constant, while Ω2 decreases. Green, red, and infrared emissions centered at 530, 550, 660, and 1530 nm were observed under excitation at 800 nm. The lifetime of the Er3+: 4I13/2 → 4I15/2 (1530 nm) transition decreases with increasing Er3+ content, reflecting how significant the non-radiative process associated with this transition is. The McCumber theory was used to calculate, from absorption cross-section, the stimulated emission cross-section of the Er3+: 4I13/2 → 4I15/2 transition. A strong re-absorption of the fluorescence at 1530 nm was also observed and analyzed. Finally, we discuss the potential use of Er3+:PbPO4 glasses in photonics devices.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-06-09T11:42:53Z No. of bitstreams: 1 alyssonmirandadefreitas.pdf: 61947422 bytes, checksum: fabd334a3f9ff790ff3a3b4c6d2016d5 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-06-26T19:59:08Z (GMT) No. of bitstreams: 1 alyssonmirandadefreitas.pdf: 61947422 bytes, checksum: fabd334a3f9ff790ff3a3b4c6d2016d5 (MD5) / Made available in DSpace on 2017-06-26T19:59:08Z (GMT). No. of bitstreams: 1 alyssonmirandadefreitas.pdf: 61947422 bytes, checksum: fabd334a3f9ff790ff3a3b4c6d2016d5 (MD5) Previous issue date: 2015-03-30 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho, propomos uma nova matriz vítrea, denominada de PZABP, de composição nominal 60P205 . 15ZnO . 5A/203 . 10Ba0 . 10Pb0, em mol %, nanoestruturada com nanocristais de ZnTe e dopada com íons de Yb3+ e avaliamos a viabilidade de utilização deste material para aplicações em dispositivos fotônicos, tais como, lasers de alta potência, fibras ópticas lasers, lasers de pulsos ultra-curtos e lasers sintonizáveis na região do infravermelho. As amostras foram produzidas através do método de fusão-resfriamento, sendo confeccionado dois conjuntos. Um deles, PZABP + xYb, foi dopado apenas com íons de Yb3+ em concentrações que variam de 0% a 10%, em wt%, com acréscimos de 1%. Outro conjunto, PZABP + 1ZnTe + xYb, foi dopado com 1% de nanocristais semicondutores de ZnTe e íons de Yb3+ em concentrações que variam de 0% a 5%, em wt%. As propriedades ópticas das amostras e as interações entre os íons de Yb3+ vizinhos e entre os nanocristais de ZnTe e os íons Yb3+ foram estudadas através das técnicas de Absorção Óptica, Fotoluminescência e Fotoluminescência Resolvida no Tempo. A Espectroscopia de Lente Térmica e a técnica de Capacidade Térmica Volumétrica, também conhecida como pc, foram utilizadas para caracterizar as propriedades térmicas das amostras. Alguns dos principais parâmetros que analisam o desempenho e o limiar de ação laser do material foram estimados a partir da determinação das seções de choque de absorção e emissão dos íons de Yb3+ quando inseridos nessa matriz. De forma geral, a matriz vítrea PZABP demonstrou-se um excelente material hospedeiro para os íons de Yb3+ por apresentar uma ampla janela óptica, ser tolerante a altas concentrações de dopantes e não formar aglomerados de íons de Yb3+, garantindo assim uma boa qualidade óptica para aplicações em fotônica. Parâmetros importantes como o tempo de vida e a eficiência quântica do material apresentaram valores comparáveis aos encontrados na literatura. Foi verificado que a presença dos nanocristais de ZnTe intensificou a emissão dos íons de Yb3+, indicando que houve transferência de energia entre os nanocristais e os íons. Com relação a análise térmica, foram encontrados valores desejáveis para aplicações que envolvem ambientes superaquecidos. A alta difusividade e condutividade térmica das amostras as permitem dissipar calor rapidamente e a baixa variação do caminho óptico com a temperatura (ds/dT) indica que o feixe não sofre desvios muito acentuados no interior da cavidade óptica. Os parâmetros de emissão laser encontrados estão comparáveis aos de outras matrizes vítreas já estudadas, embora a presença dos nanocristais de ZnTe pareça prejudicar esses parâmetros. Portanto, de acordo com os resultados encontrados e com base nas possíveis melhoras que podem ser realizadas, concluímos que a matriz vítrea PZABP nanoestruturada com nanocristais semicondutores de ZnTe e dopada com íons de Yb3+ é um material viável para aplicações em dispositivos fotônicos de alta potência. / In this work, we have proposed a new glass matrix, called PZABP, with nominal composition 60P205 . 15ZnO . 5A/203 . 10Ba0 . 10Pb0, in mol %, nanostructured with ZnTe semiconductor nanocrystals and doped with Yb3+ ions, then, we analized its availability to photonics devices application like high power lasers, optical fiber lasers, ultra-short pulses lasers and tunable lasers in the infrared region. The samples were produced by fusion method, being made two sets. One, PZABP + xYb, was doped with Yb3+ ions at various concentrations from 0% to 10%, in wt%.The other one, PZABP + 1ZnTe + xYb, was doped with semiconductors nanocrystals of ZnTe and Yb3+ ions at concentrations from 0% to 5%, in wt%. The optical properties of the samples and the interactions between neighbors Yb3+ ions and between semiconductors nanocrystals of ZnTe and Yb3+ ions were studied by Optical Absorption, Photoluminescence and Time Resolved Photoluminescence techniques. Thermal Lens Spectroscopy and Heat Volumetric Capacity, also know as pc, were used to characterize the thermal properties of the samples. The main parameters that avail the performance laser and the threshold action laser were estimated by the determination of absorption and emission cross section of the Yb3+ ions when they are inserted in this matrix. The PZABP glass matrix showed to be an excellent host material to Yb3+ ions because it present a large optical window, it is tolerant to high dopants concentration and not showed Yb3+ clusters. Important parameters like lifetime and quantum efficience showed values comparable to others found in the literature. It was verified that the presence of ZnTe nanocrystals had enhanced the emission of the Yb3+ ions, indicating that have occurred energy transfer between ZnTe nanocrystals and Yb3+ ions. Thermal properties have presented interesting values to applications that involved superheated environment. The high thermal diffusivity and high thermal conductivity allow the sample to dissipate the heat quickly. The low variation of the optical path with the temperature (ds/dT) indicate that the laser beam not strongly deviates into the optical cavity. The laser performance parameters obtained are comparable to the other glass matrix found in the literature, although the presence of the ZnTe nanocrystals seems to prejudice these parameters. According with the results found and the improvement that could be done, we have conclude that the glass matrix PZABP nanostructured with semiconductores nanocrystals of ZnTe and doped with Yb3+ ions is a viable material to application in high power photonics devices materials.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-06-08T20:19:50Z No. of bitstreams: 1 geraldohenriquessilva.pdf: 20536600 bytes, checksum: 9b626b89b88c550fa0fff1dcca169621 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-06-26T20:29:26Z (GMT) No. of bitstreams: 1 geraldohenriquessilva.pdf: 20536600 bytes, checksum: 9b626b89b88c550fa0fff1dcca169621 (MD5) / Made available in DSpace on 2017-06-26T20:29:26Z (GMT). No. of bitstreams: 1 geraldohenriquessilva.pdf: 20536600 bytes, checksum: 9b626b89b88c550fa0fff1dcca169621 (MD5) Previous issue date: 2014-02-28 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho estudou-se vidros co-dopados por meio de técnicas espectroscópicas de absorção óptica, espectroscopia Raman, fotoluminescência, fotoluminescência resolvida no tempo, lente térmica e capacidade térmica volumétrica. A classe de vidro estudada é a de vidros fosfatos denominados PZABP (P205 – ZnO – Al203 – BaO – PbO), os quais foram dopados com íons de európio (Eu3+), em diferentes concentrações, e telúrio (Te), visando o surgimento de nanopartículas semicondutoras de Telureto de Zinco (ZnTe). O objetivo desse trabalho é investigar a emissão do Eu3+ e sua interação com as nanopartículas semicondutoras no sentido de melhorar as propriedades ópticas e/ou térmicas do sistema vítreo co-dopado. Com a técnica de absorção óptica foi possível observar a alta transparência desse sistema, com uma janela óptica cobrindo a região desde o ultravioleta (em torno de 300 nm) até ao infravermelho médio (em torno de 3000 nm). Observou-se uma banda de absorbância larga centrada em torno de 540 nm quando o sistema vítreo PZABP foi dopado com Te. Essa banda foi atribuída a nanopartículas de ZnTe com comportamento de material na forma bulk. Com a técnica de fotoluminescência observou-se uma emissão avermelhada intensa atribuída aos íons de Eu3+, sendo a transição 5D0 —> 7F2 (611 nm) a mais intensa. Os parâmetros de Judd-Ofelt foram obtidos a partir dos espectros de emissão e absorção. De posse desses parâmetros, encontrou-se o tempo de vida radiativo do estado 5D0 que, juntamente com o tempo de vida experimental, permitiu a determinação da eficiência quântica. Observou-se que a mesma não sofreu uma alteração significativa em função da concentração dos íons de Eu3+ e com a presença do ZnTe. Com a técnica de lente térmica, na presença de nanopartículas de ZnTe, observou-se que a difusividade térmica (D) permaneceu praticamente constante com o aumento da concentração de Eu3+. / IIn this work we have studied co-doped glasses by means of spectroscopic techniques such as optical absorption, Raman spectroscopy, photoluminescence, time-resolved photoluminescence, thermal lens and volumetric heat capacity. The class of studied glasses was of phosphate glasses called PZABP (P2O5 – ZnO – Al203 – BaO – PbO) doped with different concentrations of europium ions (Eu3+), and tellurium (Te), to nucleation of semiconductor nanoparticles of zinc telluride (ZnTe). The goal of this work is to investigate the emission of the Eu3+ and its interaction with the semiconductor nanoparticles aiming to improve the thermo/optical properties of the glass system. With the optical absorption technique was possible to observe the high transparency of the system, which covers an optical window going from the ultraviolet region (about 300 nm) to mid-infrared (about 3000 nm). Also, was observed a large absorbance band centered around 540 nm when the glass system PZABP was doped with Te. This band was attributed to bulk-like ZnTe nanoparticles. Through the photoluminescence technique was possible to observe an intense reddened emission attributed to Eu 3+ ions, being the 5D0 —>7 F2 transition ( 611 nm) the most intense. The Judd-Ofelt parameters were obtained from the absorption and emission spectra. From these parameters, the radiative lifetime of the state 5D0 was found which together with the experimentally measured lifetime allowed the determination of the quantum efficiency. The latter does not present a significant change when the concentration of Eu3+ ions increases and with the presence of ZnTe. With the thermal lens technique, in the presence of ZnTe nanoparticles, was observed that the thermal diffusivity (D) remained almost constant with the increasing of concentration of Eu3+.

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