Afin de répondre à une demande croissante dans le domaine des télécommunications, de nombreuses recherches sont axées sur le développement de systèmes « tout optique » ou électro–optiques pour la détection, le stockage et le transfert ultra-rapides de l’information. Or, les dispositifs actuels souffrent de temps de réponse « longs» (10-9 à 10-10 s) par rapport à ceux mettant en jeu des phénomènes d’optique non linéaire (10-12 s voire 10-15 s), notamment la Génération de Seconde Harmonique (SHG). Parmi un vaste choix de matériaux optiquement non linéaires, les verres à base de TeO2 sont des candidats intéressants en raison de leur réponse non linéaire élevée (50 fois supérieure à la silice vitreuse) ainsi que de leur large domaine de transparence dans le visible ainsi que le proche IR. Par ailleurs, les verres présentent des qualités essentielles pour le développement de ces dispositifs : facilité d’élaboration, faible coût et grande diversité de composition contrairement aux monocristaux. Or, l’absence de susceptibilité non linéaire d’ordre deux dans les matériaux vitreux, du fait de leur isotropie, rend les verres inaptes à générer un doublage de fréquence d’un faisceau lumineux. Au cours de cette thèse, nous avons donc mis en œuvre la réalisation de vitrocéramiques transparentes, par cristallisation in situ ou dispersion de cristaux non centrosymétriques (permettant de générer de la SHG), et ce, par diverses techniques non conventionnelles, les verres tellurites étudiés présentant une cristallisation préférentielle de surface, liée à une nucléation hétérogène. Aussi l’élaboration de céramiques transparentes par cristallisation congruente d’un verre a été explorée. / In order to provide an answer to the growing need in means of communication, the research is pushed towards the development of all-optical or electro-optical systems for fast detection, storage or transfer of information. Meanwhile, the actual systems suffers from “long” time-response (10-9 to 10-10 s) compared to those based on nonlinear optical phenomena such as Second Harmonic Generation (SHG). Amongst a wide choice of nonlinear optical materials, TeO2-based glasses are interesting candidates because of their high nonlinear response (50 times that of silica) and their high optical transparency in the visible and near-IR range. Moreover, glasses exhibit essential qualities for the development of such systems : low cost, ease of fabrication and a wide range of chemical composition compared to single crystals. Yet, the lack of second order nonlinear susceptibility in glassy materials because of their isotropy makes them incapable to generate the frequency-doubling of a light beam. Thus, this PhD thesis consisted in the elaboration of transparent glass-ceramics by in situ crystallization or incorporation of non-centrosymmetric crystals (which generates SHG) using non-conventional technics, the tellurite glasses studied showing evidence of surface crystallization due to heterogeneous nucleation. Finally, we also investigated the elaboration of transparent TeO2-based ceramics by congruent crystallization of glass.

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-05-05T21:22:10Z No. of bitstreams: 1 MilenaLima.pdf: 3266309 bytes, checksum: 9b2725b434fc3fa33272819ef5426046 (MD5) / Made available in DSpace on 2017-05-05T21:22:10Z (GMT). No. of bitstreams: 1 MilenaLima.pdf: 3266309 bytes, checksum: 9b2725b434fc3fa33272819ef5426046 (MD5) Previous issue date: 2016-11-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPQ) / Fundação de Amparo à Pesquisa e ao Desenvolvimento Científico e Tecnológico do Maranhão (FAPEMA) / This research presents the synthesis and characterization of Yb3+ - doped calcium borotellurite glasses (Yb:CaBTeX). Density, DRX, DTA, specific heat, refractive index, electronic polarizability, optical absorption, luminescence and lifetime measurements were performed to investigate the structural, thermal, optical and spectroscopic properties of Yb:CaBTeX as a function of TeO2 content. The density increased with TeO2 concentration and DRX pattern confirmed the amorphous structure of all samples. The FTIR and Raman spectroscopic indicate the presence of TeO4, TeO3, TeO3+1, BO4 and BO3 units in the network structure. The increase of TeO2 increases the NBO’s and decreases the phonon energy. The DTA analysis shows a decrease of glass transition temperature (Tg) and crystallization temperature (Tx) with increase of TeO2. Also, the addition of TeO2 increases the thermal stability, which presented values above 100 °C for all samples. The specific heat values show a decrease with TeO2 increase, because the bonding enthalpy Te – O is smaller than B – O, consuming less energy to be broken or to vibrate. The refractive index and electronic polarizability values increase with TeO2 content, because Te4+ ions presents larger polarizability than B3+ and Ca2+ ions. The energy band gap and emission intensity of Yb3+ decrease with the increase of TeO2 content, due to the increase of NBO’s and the decrease number of ions per cubic centimeter (N), respectively. There was no variation within the errors, for the radiative lifetime of the Yb:CaBTeX samples. The absorption and emission cross section do not present variation with TeO2 addition and the calculated values are higher than tellurite and phosphate glasses. The analyses showed that Yb3+-doped calcium borotellurite glass feature good combinations of properties, which make them good candidates to be used as photonics devices. / Neste trabalho foram realizadas a síntese e caracterização dos vidros Cálcio Boroteluretos dopados com óxido de itérbio (Yb2O3). As medidas de densidade, difratometria de raios-X, Espectroscopia Raman, Espectroscopia no Infravermelho com Transformada de Fourier (FTIR), Análise Térmica Diferencial (DTA), calor específico, índice de refração, absorção óptica, luminescência e tempo de vida foram realizadas para estudar a influência da concentração de TeO2 nas propriedades estruturais, térmicas, ópticas e espectroscópicas da série vítrea. Também foram calculados os parâmetros polarizabilidade eletrônica e seção de choque de absorção e emissão. Os difratogramas de DRX confirmaram a natureza amorfa de todas as amostras. A densidade e o volume molar aumentaram com o aumento do conteúdo de TeO2. Os resultados das espectroscopias Raman e FTIR mostraram que a rede vítrea é formada por estruturas BO3, BO4, TeO3, TeO3+1 e TeO4, que houve uma diminuição na energia de fônons e um aumento dos NBO’s com o aumento da concentração de TeO2. Os resultados de DTA mostraram a diminuição das temperaturas de transição vítrea (Tg) e temperatura de início de cristalização (Tx), e um aumento na estabilidade térmica (Tx-Tg), com valores acima de 100 °C para todas as amostras, com o aumento da quantidade de TeO2. O calor específico apresentou uma redução com o aumento de TeO2 devido à entalpia de ligação Te-O ser menor quando comparada com a entalpia de ligação B-O, necessitando de menos energia para vibrar ou ser rompida. Os valores de índice de refração e polarizabilidade eletrônica aumentam com o maior teor de TeO2, esta última explicada pela maior polarizabilidade eletrônica do íons Te4+ quando comparado aos íonsB3+ e Ca2+. A absorção óptica dos vidros Yb:CaBTeX apresentou uma banda na região entre 900-1050 característica do Yb3+, comprovando a dopagem do material. O band gap óptico e a intensidade de emissão diminuíram com o aumento do conteúdo de TeO2, devido ao aumento dos NBO’s e a diminuição dos íons por centímetro cúbico (N). O tempo de vida não sofreu variação, dentro do erro, com o aumento da concentração de TeO2. Os valores para seção de choque de absorção e emissão não sofrem variações significativas com o aumento do teor de TeO2, apresentando altos valores quando comparados aos vidros teluretos e fosfatos. As análises dos dados mostraram que os vidros Yb:CaBTeX apresentam boas propriedades que os tornam bons candidatos a serem utilizados como dispositivos fotônicos.

Ce travail a pour but d’améliorer la description structurale du verre de TeO2 pur et d’étudier en profondeur la structure de la phase désordonnée δ-TeO2 au moyen de la dynamique moléculaire (DM). Nous avons établi des potentiels interatomiques (IAP), simples mais non triviaux, prenant en compte la polarisabilité des atomes de tellure et d’oxygène à l'aide du modèle cœur-coquille. Nous avons démontré le rôle important de la paire libre électronique de l'atome de Te dans la formation d'unités asymétriques TeOx. Les IAPs précis reproduisent 17 structures cristallines à base de TeO2 et sont appropriés pour les simulations par DM des systèmes désordonnés. Les simulations des structures de la phase vitreuse pure et de δ-TeO2 ont été effectuées par DM. Il a été démontré que le verre de TeO2 est principalement constitué d'unités structurales TeO3 et TeO4, et un grand nombre d'atomes d’oxygène non-pontant (NBO) est observé. La coordinence des atomes de tellure est plus faible dans le verre que dans les structures cristallines pures.Dans la phase δ-TeO2, les atomes de tellure forment un réseau cristallin (CFC) bien défini et les atomes d'oxygène présentent un grand désordre de position. Cette phase est caractérisée par une population d’unités structurales, une coordinence des atomes de tellure et une proportion d'atomes d’oxygène non pontant typique du verre. Par conséquent, la structure δ-TeO2 est plus proche de celle du verre que des structures d'autres polymorphes cristallines de TeO2 pures. / This work aims to improve the structural description of the pure TeO2 glass and to give a deep insight into the structure of the disordered δ-TeO2 phase by means of molecular dynamics (MD) simulations.We derived simple but nontrivial interatomic potentials (IAPs), which take into account the polarisability of tellurium and oxygen atoms using the core-shell model. We demonstrated the important role of the electronic lone pair of the tellurium atoms in the formation of asymmetrical TeOx units. The accurate IAPs is able to reproduce 17 crystalline TeO2-based structures and are appropriate for MD simulations of disordered systems.The MD simulations of the pure glass and δ-TeO2 phase structures were carried out. It was demonstrated that the TeO2-glass consists of mainly TeO3 and TeO4 structural units and a large number of non-bridging oxygen (NBO) atoms is observed. The coordination number of the tellurium atoms in the glass is less than in the pure crystalline structures.In the δ-TeO2 phase, the tellurium atoms form a well-defined crystalline (FCC) lattice and the oxygen atoms exhibit a large positional disorder. This phase has a structural units distribution and a tellurium coordination number and a proportion of NBO atoms similar to those of the glass. Hence, the structure of δ-TeO2 is closer to that of glass than to the structures of other pure TeO2 crystalline polymorphs.

Orientador: José de los Santos Guerra / Resumo: Os materiais vítreos a base de TeO2 têm sido amplamente estudados e suas potencialidades requerem particular atenção para o desenvolvimento de novos sistemas vitrocerâmicos. Neste trabalho, com o objetivo de formar nanocristais de BaTiO3 (na fase tetragonal) através da estequiometria do sistema xBaO–xTiO2–(100–2x)TeO2 (BTT), tratamentos isotérmicos foram realizados sob diferentes condições. Desse modo, foram investigadas as propriedades físicas do sistema BTT para as composições x = 7,5, 10,0 e 12,5 mol%, de nomenclaturas 85BTT, 80BTT e 75BTT, respectivamente. As amostras foram obtidas pelo método convencional de fusão, seguido de um rápido resfriamento (quenching). Particularmente, suas propriedades térmicas, estruturais e óticas foram analisadas a partir de Análise Térmica Diferencial (DTA), Difração de raios-X (DRX), Espectroscopia Raman (ER) e de Absorção Ótica (AO). Os resultados revelaram uma forte influência das concentrações de BaO-TiO2 nas propriedades estudadas, que pode ser associada à quebra de simetria da unidade estrutural elementar (TeO4), devido à variação estrutural TeO4TeO3+1TeO3, ao caráter covalente das ligações TeO, a presença do par de elétrons livres na camada de valência do TeO2 e, consequentemente, à formação de oxigênios não ligantes (NBO’s). As bandas de cortes no UV-Vis apresentaram absorção fundamental na região de 400-450nm, onde a rede mais polimerizada da composição 80BTT proporcionou os valores mais elevados do gap indireto (Ei = 2,87eV) e ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: TeO2-based glassy materials have been extensively studied and their potentialities require particular attention for the development of new ceramic-glass materials. In this work, viewing the formation of tetragonal BaTiO3 nanocrystals by considering the xBaO–xTiO2–(100–2x)TeO2 (BTT) stoichiometry formula, isothermal treatments were performed under different conditions. Thus, the physical properties of the BTT system were investigated for compositions with x = 7.5, 10.0 and 12.5 mol%, hereafter labeled as 85BTT, 80BTT and 75BTT, respectively. The samples were obtained by the conventional fusion method followed by rapid cooling (known as the quenching method). Particularly, the thermal, structural and optical properties were studied from Differential Thermal Analysis (DTA), X-ray Diffraction (XRD), Raman Spectroscopy and Optical Absorption (OA) analyses. The results showed a strong influence of the BaO-TiO2 concentrations on the studied properties, which could be related to the symmetry breaking of the elemental structural unit (TeO4), due to the TeO4→TeO3+1→TeO3 structural variation, the covalent character of the Te−O bonds, the presence of the lone-pair valence electrons in the TeO2 and, consequently, the formation of non-binding oxygen (NBO's). The UV-Vis cut-off bands revealed the fundamental absorption in the 400-450nm region, where the most polymerized network of the 80BTT samples has provided the highest indirect (Ei = 2.87eV) and direct (Ed = 2.96eV) gap values. The resu... (Complete abstract click electronic access below) / Doutor

Orientador: João Carlos Silos Moraes / Resumo: O presente trabalho tem como objetivo a síntese e caracterização estrutural de filmes finos a base de TeO2 usando o método Pechini. Os filmes finos foram produzidos seguindo a estequiometria 80TeO2–20Li2O (% molar), utilizando como precursores metálicos o ácido telúrico (H6TeO6) e o carbonato de lítio (Li2CO3). Os materiais precursores foram solubilizados em solução aquosa de ácido cítrico sob aquecimento para obtenção de um citrato metálico, o qual foi acrescido de etilenoglicol para polimerização. A resina polimérica obtida foi depositada sobre dois diferentes substratos, vidro e silício cristalino, pela técnica de spin-coating, para a obtenção dos filmes finos. Em substratos de vidro, a pirólise ocorreu a 300°C e o tratamento térmico foi realizado à 400°C e nos substratos de Si, os filmes foram pirolisados a 500°C e tratados termicamente em 600°C. A caracterização dos filmes foi realizada por meio das técnicas de difração de raios-X, microscopia eletrônica de varredura, espectroscopia de energia dispersiva e Raman. Os filmes obtidos apresentaram espessuras da ordem de micro a nanômetros e, dos dados de Espectroscopia de Energia Dispersiva, foi possível acompanhar a transformação do Te metálico para as fases do TeO2. Dos dados de difração de raios X e Raman foi possível identificar e observar a transição entre as fases γ e α-TeO2. A qualidade dos filmes finos obtidos usando a rota estabelecida neste trabalho, demonstra a viabilidade da produção de filmes finos a base de tel... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The objective of this work is the synthesis and structural characterization of thin films based on TeO2 using the Pechini method. The thin films were produced following the stoichiometry 80TeO2-20Li2O (mol%) using telluric acid (H6TeO6) and lithium carbonate (Li2CO3) as metallic precursors. The precursor materials were solubilized in aqueous solution of citric acid under heating to obtain a metal citrate, which was added with ethylene glycol for polymerization. The obtained polymer resin was deposited on two different substrates, glass and crystalline silicon, by the spin-coating technique, to obtain the thin films. On glass substrates, the pyrolysis occurred at 300°C and the heat treatment was performed at 400°C, and on the Si substrates, the films were pyrolyzed at 500°C and thermally treated at 600°C. The films were characterized by X-ray diffraction, scanning electron microscopy, dispersive energy and Raman spectroscopy. The films obtained presented thicknesses of the order of micro to nanometers and, from the data of Dispersive Energy Spectroscopy, it was possible to follow the transformation of the metallic Te to the phases of TeO2. From the X-ray and Raman diffraction data it was possible to identify and observe the transition between the γ and α-TeO2 phases. The quality of the thin films obtained through the route established in this work, demonstrates the practicability of the preparation of tellurium based thin films by the Pechini method. / Mestre

Ce travail est une contribution à la compréhension de la structure à courte et moyenne distance des verres à base de TeO₂ via de nouveaux verres au sein des systèmes TeO₂-TiO₂-WO₃ (TTxWy) et TeO₂-NbO₂ ̩₅-WO₃ (TNxWy). De pertinentes corrélations sont révélées entre leurs propriétés structurales (en utilisant la spectroscopie Raman) et optiques. Globalement, l’ajout de TiO₂, WO₃ ou NbO₂ ̩₅ n’engendre aucune évolution structurale brutale. L’ajout de TiO2 induit une séparation de phases entre les régions amorphes riches en TiO2 et le réseau riche en TeO2. Cette interprétation est en accord avec le comportement structural prédit par la théorie de Dietzel sur la force de champ cationique. L’ajout de WO3 entraîne l’apparition (i) d’octaèdres WO₆ uniformément dispersés à travers le réseau des ponts Te–O–Te (pour de faibles teneurs en WO₃) et (ii) de régions riches en WO3 (pour des teneurs plus importantes en WO₃). L’ajout de NbO₂ ̩₅ engendre (i) une faible dépolymérisation structurale du réseau Te–O–Te et (ii) l’apparition des régions riches en NbO₂ ̩₅. Les verres étudiés sont dotés de forts indices de réfraction linéaires (2.19 dans TTxWy et 2.13 dans TNxWy en moyenne) et de remarquables susceptibilités non linéaires χ(3) (7.03 *10-13 esu dans TTxWy et 5.48 *10-13 esu dans TNxWy en moyenne, i.e., ~47 et ~37 fois plus élevées que la valeur de χ(3) du verre SiO₂). / In this work, we present a contribution to the understanding of the short- to medium-range structure of TeO₂-based glasses via new glasses within the TeO₂-TiO₂-WO₃ (TTxWy) and TeO₂-NbO₂ ̩₅-WO₃ (TNxWy) systems. Consistent correlations are revealed between their structural (using Raman spectroscopy) and optical properties. Globally, no striking structural evolutions take place upon adding TiO₂, WO₃ or NbO₂ ̩₅. Adding TiO2 results in a phase-separation between amorphous TiO₂-rich regions and TeO2-rich network, in harmony with the predicted structural behavior on the basis of Dietzel’s cationic field strength theory. Adding WO₃ leads to (i) uniformly dispersed WO₆ octahedra throughout the Te–O–Te network (at low WO₃ contents) and (ii) amorphous WO₃-rich regions (at higher WO₃ contents). Adding NbO₂ ̩₅ engenders (i) a weak structural depolymerization of the Te–O–Te network and (ii) occurrence of NbO₂ ̩₅-rich regions. The investigated glasses exhibit high linear refractive indices (averages of 2.19 in TTxWy and 2.13 in TNxWy) and remarkable nonlinear susceptibilities χ(3) (averages of 7.03 *10-13 esu in TTxWy and 5.48 *10-13 esu in TNxWy, i.e., ~47 and ~37 times higher than χ(3) of SiO₂ glass).

Les verres se placent actuellement parmi les candidats potentiels pour des applications en optoélectronique (transport de l' information par fibres optiques, commutation...). Dans la perspective du développement de tels matériaux, cette thèse analyse l'origine du fort effet Kerr optique des verres a base d'oxyde de tellure TeO2. Des calculs ab initio ont permis d'établir des corrélations entre la structure locale des entités polarisables TeOn et leur activité optique. En outre, le phénomène de génération de seconde harmonique dans les verres a été appréhendé dans le cas particulier de la silice.