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No. of bitstreams: 2 Tese- Fausto de Melo Faria Filho - 2017.pdf: 6580669 bytes, checksum: 29a18b3c0e94bc8b3bf1f3b87f339ee1 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-04-12 / The objective of this thesis is study aluminogermanate and aluminoborate compounds containing lanthanide ions for photonic applications, especially light emitting diodes, as phosphors. Samples were prepared by sol-gel and polymeric precursor method (Pechini method). It was studied pure and doped Al6Ge2O13 with 1 mol% Eu3+ or Er3+ , heat treated at 1000 °C; 1 mol% Eu3+ doped xAl2O3+(1-x)B2O3, for x values: 0.33; 0.50; 0.60; 0.66; 0.75 and 0.80 under heat treatments at 800, 900 or 1000 °C; and the Al4B2O9 phase with xNd3+/ yYb3+, where x, y = 1, 0; 1, 1; 1, 2; 1, 4; 1, 8; 0, 1; 2, 1; 4, 1 and 8, 1, heat treated at 900 °C. The powders samples were characterized by X-ray diffraction, infrared vibrational spectroscopy, thermal analysis, and transmission electron microscopy. Diffuse reflectance spectra and photoluminescence emissions were collected under excitation at 394 nm for Eu3+ doped samples, at 378 and 977 nm for Er3+ doped samples, at 804 nm for Nd3+/Yb3+ doped samples and at 365 nm for pure samples. The Er3+ or Eu3+ doped aluminogermanate sample presented the Al6Ge2O13 crystalline phase identified by JCPDS card number 71-1061 after annealings at high temperatures. Absorption spectra in the infrared region showed Al-O-Ge and Al-O type bonds. The Eu3+ doped Al6Ge2O13 samples when excited at 394 nm showed red emission and the spectra analysis lead us to conclude that the lanthanides were located in a homogeneous environment with low symmetry. The Er3+ doped Al6Ge2O13 sample showed emission band in the infrared region with full width at half maximum of around 48 nm when excited at 977 nm. The band gap values were determined being between 4.19 and 4.30 eV. The Eu3+ doped xAl2O3+(1-x)B2O3 compositions presented the crystalline phase Al4B2O9 identified by JCPDS card number 29-0010. AlO6, AlO4, BO4 and BO3 groups were identified by FTIR technique. For these compositions, the emission spectra in the visible region showed a homogeneous environment with low symmetry. The Eu3+ doped 0.66Al2O3+0.34B2O3 sample possess the highest photoluminescence emission, after heat treatments at 900 °C . The lifetime of the Eu3+ 5D0 excited level were between 1.4 and 2.1 ms, depending on the B2O3 concentration and annealing temperature. The optical band gap was also determined having values between 3.72 and 4.42 eV. The Nd3+/Yb3+ doped Al4B2O9 samples present an efficient energy transfer between lanthanide ions and the best relative concentration was 1Nd3+ / 2Yb3+. The decay time of the emission at 1080 nm (975 nm) as function the Nd3+ concentration shows a maximum value around 120 μs at concentration of 4 mol% (around 200 μs for 2 mol%). On the other hand, changing the Yb3+concentration, the maximum decay time for emission at 1080 nm (975 nm) was around 100 μs (175 μs) for 1 mol% of Yb3+. In short, the materials studied are excellent candidates for application as luminophores in various technologies, such as LED´s and displays. / A presente tese tem como principal objetivo estudar matrizes nanocristalinas de compostos germanatos e boratos contendo íons lantanídeos visando aplicações em fotônica, especialmente emissores de luz (fósforos). Foram preparadas pelo processo sol-gel e método dos precursores poliméricos (método Pechini), amostras com as seguintes composições: Al6Ge2O13 sem dopante e dopada com 1% em mol de Eu3+ ou Er3+, tratadas termicamente a 1000 °C, xAl2O3+(1-x)B2O3 dopada com 1% em mol de Eu3+ para valores de x iguais a 0,33; 0,50; 0,60; 0,66; 0,75 e 0,80 e tratamentos térmicos de 800, 900 ou 1000 °C e a fase Al4B2O9 dopada com xNd3+/yYb3+ (onde x,y = 1,0; 1,1; 1,2; 1,4; 1,8; 0,1; 2,1; 4,1 e 8,1) tratada termicamente a 900 °C. As amostras na forma de pós nanoestruturados foram caracterizadas por difração de raios X, espectroscopia vibracional na região do infravermelho, análise térmica e microscopia eletrônica de transmissão. Coletou-se também espectros de refletância difusa e emissão óptica fotoluminescente sob excitação de 394 nm para amostras dopadas com íons Eu3+, de 378 e 977 nm para amostras dopadas com íons Er3+, de 804 nm para amostras dopadas com Nd3+/Yb3+ e 365 nm para amostras sem dopantes. A amostra aluminogermanato dopada com íons Er3+ ou Eu3+ apresentou a fase cristalina Al6Ge2O13 identificada com a ficha JCPDS número 71-1061 após tratamentos térmicos a altas temperaturas. Espectros de absorção na região do infravermelho mostraram grupos AlO4, AlO6 e GeO4. A amostra Al6Ge2O13 dopada com Eu3+ quando excitada em 394 nm apresentou emissão no vermelho e uma análise do espectro mostrou que o terra-rara se localizava em um ambiente homogêneo e de baixa simetria. A amostra Al6Ge2O13 dopada com Er3+ quando excitada em 977 nm, apresentou emissão com largura à meia altura em torno de 48 nm. O band gap foi determinado e seus valores variaram entre 4,19 e 4,30 eV. A amostra de composição xAl2O3+(1-x)B2O3 dopada com Eu3+ apresentou a fase cristalina Al4B2O9 identificada com a ficha JCPDS número 29-0010. Grupos AlO6, AlO4, BO4 e BO3 foram identificados pelos espectros de absorção na região do infravermelho. Os espectros de emissão na região do visível mostraram um ambiente homogêneo de baixa simetria e a amostra com maior emissão foi a de composição 0,66Al2O3+0,34B2O3 tratada a 900 °C (x=0,66). Foi medido o tempo de vida da transição do estado 5D0 dos íons Eu3+, e seus valores estão entre 1,4 e 2,1 ms. O band gap das amostras também foi determinado e seus valores ficaram entre 3,72 e 4,42 eV. Nas amostras dopadas com Nd3+/Yb3+, uma eficiente transferência de energia entre os íons foi observada e a melhor concentração relativa dos terras-raras foi de 1Nd3+ para 2Yb3+. Em suma, os materiais estudados são excelentes candidatos para aplicação como luminóforos em diversas tecnologias, tais como diodos emissores de luz (LED´s) e displays.

Ce travail de thèse porte sur la synthèse et la caractérisation de matériaux amorphes et cristallin sous forme de poudres et de couche minces du systhème Er2O3-Y2O3-Al2O3-B2O3. L'objectif principal du travail a été de préparer des couches minces amorphes dopées erbium dont la composition est proche de YAl3(BO3)4 (YAB), en vue de la réalisation d'amplificateurs pour l'optique guidée. Pour la synthèse des échantillons, les méthodes des précurseurs polymériques et sol-gel ont été utilisées. Les caractérisations thermiques, structurales et optiques des échantillons, sous forme de poudre et de couches minces, ont été réalisées par l'analyse thermogravimétrique, microcalorimétrie différentielle, diffraction des rayons X, spectroscopie infrarouge à transformé de Fourier, spectroscopie Raman, microscopie électronique à balayage, microscopie à force atomique, spectroscopie “m-line”, et de luminescence. L'ensemble de ces résultats nous a permis de parfaitement contrôler l'élaboration de couches minces vitreuses de compositions Y1-xErxAl3(BO3)4 (x = 0,02; 0,05; 0,1; 0,3 et 0,5) qui présentent une très bonne homogénéité chimiques et de bonnes propriétés optiques. Les couches minces recuites à des températures comprises entre Tg et Tc, présentent les meilleures conditions pour obtenir des dépôts très denses et homogènes, conduisant à de bonnes efficacité de guidage, d'émission de luminescente et de durées de vie. Les couches vitreuses de composition Y0,9Er0,1Al3(BO3)4 et d'épaisseurs comprises entre 500 et 800 nm sont des guides d'onde monomodes qui présentent durées de vie comparables à d'autres systèmes borates amorphes. Ces résultats confirment la possibilité d'utilisation de ces couches amorphes comme amplificateurs pour l'optique guidée.

Novel open-framework germanates and vanadoborates, which are constructed from typical types of clusters, have been synthesized based on different strategies. The crystal structures are solved by using single crystal X-ray diffraction (SXRD) technique or by combined techniques. Additionally, the structures of two open-framework materials, PKU-3 and PKU-16, are determined from nano-sized crystals by rotation electron diffraction (RED) combined with powder X-ray diffraction (PXRD). This thesis serves as an introduction to synthesis of open-framework germanates and vanadoborates based on different design strategies. Two germanates are obtained; SU-74 is achieved by employing a novel structure directing agent (SDA), SUT-8 is achieved by assembling the novel structure building units (SBUs) of Co@Ge14 with the introduction of cobalt ions in the synthesis. Four strategies are successfully used in construction of open-framework vanadoborates: using metal-oxo polyhedra as the linkages in SUT-6; applying the scale chemistry approach in SUT-7; employing metal-organic complexes as the linkages in SUT-12, SUT-13, SUT-14; and introducing covalent bond organic linkages into SUT-10 and SUT-11. Single crystal X-ray diffraction is used to conduct the structure determination in combination with other techniques. Furthermore, the structures of two open-framework materials, an aluminoborate PKU-3 and a germanosilicate PKU-16, are solved from nano-sized crystals using RED data. The structures are further confirmed by Rietveld refinement against PXRD data. The advantages of the RED techniques are demonstrated in two aspects. In PKU-3, the presence of seriously preferred orientation and light elements in the structure makes it difficult for structure determination by PXRD, but it is easier by RED. In PKU-16, the RED technique is used to determine its structure from the as-synthesized multi-phasic sample containing nano-sized crystals. After the structure of PKU-16 has been solved, the synthesis of this interesting phase can be optimized and pure PKU-16 can be obtained. Keywords: Open-framework, germanates, vanadoborates, aluminoborates, germanosilicates, crystal structure, hydrothermal synthesis, single crystal X-ray diffraction, rotation electron diffraction, powder X-ray diffraction

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.

Open-framework inorganic materials constitute an important area of study in materials chemistry, because of their potential applications in areas such as sorption and catalysis. After the discovery of nanoporous aluminium phosphates (AlPOs) by Flanigen et al in 1982, there has been a tremendous growth in the area of porous solids that are based on phosphates. Apart from phosphates, phosphites, arsenates, sulfates, sulfites, selenates, selenites etc. have also been investigated. In addition to the different anions, the framework compounds now encompass almost all the elements of the periodic table. The compounds exhibit wide variety and structural diversity. New building units, such as thiosulfate and borate have also been explored as a network builder in the formation of framework structures. In this thesis, the results of the investigations on open-framework metal thiosulfates, metal borates and metal sulfates are presented. The studies are aimed not only at the synthesis of the new compounds based on the new anions, but also their possible applications. In Chapter 1 of the thesis an overview of inorganic open-framework materials with different anions is presented. In Chapter 2 (Part A), the synthesis, structure and transformation of inorganic-organic hybrid open-framework cadmium thiosulfate are presented. The lack of stability of the thiosulfate ion in solution prompted the exploration of new approaches such as low temperature solvothermal methods, use of rigid linkers etc. The transformations of lower to higher dimensional structures have been accomplished. The possible mechanisms for such transformations were investigated. In Part B, the physical and chemical properties of the hybrid cadmium thiosulfate frameworks are presented. The studies indicate that the anionic dyes selectively adsorb on the compounds in the water medium and also desorb reasonably in alcoholic medium. The cadmium thiosulfate compounds appear to be reasonable photocalysts for the photodecomposition of the cationic dyes under UV irradiation as well as under sunlight with good recyclability. The compounds also exhibit heterogeneous catalytic behavior (Lewis acidity) for the cyanosilylation of the imines. In Chapter 3, a new family of organically templated open-framework borate materials is presented. The zinc and aluminoborate structures, prepared in the present study, are rationalized using the HSAB theory. The [B4O9H2] units polymerize differently to form different zinc borate structures. The amine molecules act as a ligand by binding with the metal. The nature of the amine appears to control the dimensionality of the final zinc borate structures. The zinc borate compounds exhibit absorption of UV-light (λ = 365 nm) suggesting that the zinc borate compounds could be exploited for UV-blocking applications. Organically templated aluminoborates have connectivities between the Al3+ ions and the [B5O10] cyclic pentaborate units. The aluminoborate structures exhibit graphite layer and three-dimensional diamond structure. Detailed studies and comparison of the various amine templated open-framework aluminoborate structures reveals subtle relationships between the organic amines (shape and length of the amines) and the final framework structures. In Chapter 3, the synthesis, structure and catalytic studies of a variety of cadmium sulfate phases have been carried out. Polyazaheterocyclic ligands were employed to study their possible role in the formation of such structures. All the compounds have structures built up by the connectivity involving the cadmium octahedra and the sulfate tetrahedra in which the heterocyclic organic molecules act as the ligand. The connectivity between the Cd2+ and (SO4)2− ions form one-, two-and three-dimensionally extended cadmium sulfate phases, though the starting source is cadmium sulfate (CdSO4.8/3H2O) in all the cases. The connectivity between Cd2+ ion and the heterocyclic ligand also gives rise to one-and two-dimensional structures. The interconnectivity between the two units gives rise to the final observed structure. As part of the study, a variety of properties i.e. adsorption-desorption, photocatalytic degradation and cyanosilylation reaction, exhibited by the cadmium sulfate compounds have been investigated and the properties are comparable to the cadmium thiosulfate phases. AlPOs are well known for their many important properties. The wide varieties in their structures and heterogeneous catalytic properties have been extensively investigated. The photocatalytic behaviors, on the contrary, have not been investigated in detail. The photocatalytic properties of the metal-doped AlPOs, for the photodegrdation of organic dyes have been investigated in the Chapter 5. The metal ions (Mg2+, Zn2+ and Co2+) have been substituted in place of Al3+ and Ti4+ in place of both the Al3+ and P5+ in a variety in AlPO structures and the synthesized phases are characterized by a variety of techniques. Photodecomposition studies of organic dye molecules under UV-light were carried out in aqueous medium. The studies suggest that the photocatalytic activity is reasonable and appears to depend on the dopant concentration. Ti-substituted phase exhibits the maximum catalytic activity.

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.