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Comme le trafic de données continue à augmenter rapidement, une grande capacité de transmission sera inévitablement requise pour les systèmes de communications par fibre optique. De nouvelles technologies ont été développées pour assurer une bonne qualité de transfert de l'information. Dans ce contexte, les composants optiques tout fibres occupent un rôle important pour diminuer les pertes de propagation, d'insertion et de réflexion dans une chaîne de transmission optique. Le rotateur de Faraday est conçu pour être utilisé comme isolateur et éviter les retours des faisceaux dans les lasers de haute puissance. Il est développé à base de fibre monomode pour des longueurs d'ondes inférieures à 1μm. La motivation de ce travail est d'explorer de nouvelles matrices vitreuses avec une grande réponse magnéto-optique dans la troisième fenêtre de télécommunications (1.55 μm) et d'étudier la possibilité d'avoir des fibres optiques "few mode". Dans ce sens, les verres hautement dopés en terbium sont considérés les meilleurs candidats. Toutefois leur usage est limité dans les fibres existantes vu que la concentration en ions e terre rares en terbium ne dépasse pas 27% mol dans la matrice vitreuse. Dans ce travail, on présentera plusieurs compositions vitreuses explorées dans différentes matrices de silice, de phosphate et de fluorure. Des verres contenant jusqu'à 30% mol d'oxyde de terbium dans un verre de silice et jusqu'à 40% mol de terbium fluoré dans des verres fluorés ont été obtenus dans le but de réaliser une fibre optique à deux modes de propagation à 1.55 μm. Les caractéristiques thermiques, optiques et des mesures de la constante de Verdet ont été faites sur l'ensemble des verres synthétisés en fonction de la concentration afin de comparer l'efficacité de la transmission magnéto-optique différents type de matrices. / As data traffic continues to rapidly increase, high transmission capacity will be required for fiber optic communications systems. New technologies have been developed to ensure good quality of information transfer. In this context, all-fiber optical components play an important role in reducing the propagation, insertion and reflection losses in an optical transmission link. The Faraday rotator is designed for useas an insulator in order to minimize parasitic back reflections in high power lasers. It is developed based on singlemode fiber for wavelengths less than 1μm. The motivation of this work is to explore new vitreous matrices with a large magneto-optical response in the third telecommunications window (1.55 μm) and to study the possibility of having "few mode" optical fibers. In this sens, highly doped terbium glasses are considered the best candidates. However, the solubility of terbium ions in silica glass fibers is limited to 27%, then the exploration for other glass compositions is necessary. In this work, several glass compositions have been explored in different matrices of silica, phosphate and fluoride. Glasses containing up to 30% mol of terbium oxyde in a silica glass and up to 40% by mol of terbium fluoride in fluoride glasses have been obtained in order to produce a fiber with two progagation modes at 1.55 μm. Thermal, optical and Verdet constant measurements were made on all the glasses synthesized according to their concentration in order to compare the magneto-optical transmission efficiency of different types of matrices.

Le premier chapitre de cette thèse présente l’intérêt et la problématique de la fonctionnalisation du graphène. L’état de l’art actuel de cette thématique est présenté. Dans un deuxième chapitre, nous discutons de façon détaillée des techniques expérimentales. Le chapitre 3 est centré sur la modification du graphène par réaction de cycloaddition par molécules dérivées de maleimides. Dans cette étude, nous démontrons le greffage covalent de molécules sur graphène épitaxié sans défaut sur SiC, ainsi qu’une tendance d’ouverture de bande interdite à l’aide de caractérisations par spectroscopie Raman, XPS, ARPS et STM. L’augmentation du rapport ID /IG des pics Raman et des liaisons sp3 sur l’échantillon en fonction de la durée de réaction chimique confirme le greffage. Par analogie avec les bords de marche de type « zigzag » ou « armchair », l’étude des ondes de densité de charge générées sur le graphène par les molécules permet de déterminer la nature des sous-réseaux mis en jeu lors du greffage. Dans le chapitre 4, nous étudions l’intercalation du terbium dans le graphène épitaxié. Après intercalation, l’ARPES montre une structure de bande complexe dont une composante correspond à une monocouche de graphène fortement dopée n. Nous avons pu isoler cette composante et montrer qu’elle provient du découplage de la couche tampon du substrat par le Terbium. Ces résultats sont confirmés par les données XPS. Le graphène avec Terbium intercalé produit également un réseau de lignes visibles par imagerie STM, qui a l’échelle atomique à basse tension montrent les 6 atomes de carbone de la structure en nid d’abeille, confirmant ainsi la transformation de la couche tampon en graphène. / The first chapter of this thesis explains the general motivation and problematic of graphene functionalization. It presents the state of the art of current research in this field. In the second chapter we discuss the experimental techniques in detail. Chapter 3 of this thesis work focuses on covalent modification of graphene by cycloaddition reaction of maleimide derivative molecules. In these studies we have confirmed the grafting of molecules on epitaxial defect free graphene on SiC and a tendency to open a gap with the help of Raman spectroscopy, XPS, ARPES and STM studies. An increase in the ID /IG ratio for Raman signature and sp3 bonding on the sample with increasing reaction time confirmed the reaction of molecules. By drawing an analogy with the standing waves obtained on armchair step edges of graphene and standing waves generated by molecules it was possible to determine the location of grafted molecules on the graphene lattice. In chapter 4, studies on terbium intercalation of epitaxial graphene are discussed. After intercalation a complex band structure was observed by ARPES with one spectra corresponding to highly n-doped graphene monolayer. We were able to isolate this highly n-doped graphene and confirmed its origin from decoupling of buffer layer and making it graphene like. These results are also supported by the XPS data. STM images on Terbium intercalated on buffer layer samples showed an interesting pattern of lines, atomic resolution scans at low bias voltage on these lines showed 6 atoms of hexagon confirming the transformation of buffer layer into graphene layer.

The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from PDF of title page (University of Missouri--Columbia, viewed on April 6, 2010). Vita. Thesis advisor: Mark Milanick "June 2008" Includes bibliographical references

O presente trabalho aborda a síntese e caracterização de complexos benzenotricarboxilatos de íons Eu3+, Gd3+ e Tb3+, com o intuito de investigar suas características químicas e estruturais e correlacioná-las com as propriedades fotoluminescentes. Os complexos benzenotricarboxilato [TR(BTC)(H2O)n] foram sintetizados em solução aquosa, e apresentaram-se na forma de pós brancos, não-higroscópicos e insolúveis em solventes polares ou apolares. Os complexos com o ligante EMA se mostraram isomórficos e com grau de hidratação igual a dois. Os complexos com o ligante TLA também apresentaram isomorfismo, mas com estrutura cristalina diferente da dos complexos com os outros ligantes. Os complexos [Eu(TMA)(H2O)6] e [Gd(TMA)(H2O)6] apresentaram a mesma estrutura cristalina; entretanto, o complexo [Tb(TMA)] se mostrou anidro, o que foi confirmado pela termoanálise. Os espectros de absorção na região do invravermelho dos complexos evidenciaram que os ligantes BTC3- se coordenam aos íons TR3+ através dos grupos carboxilato desprotonados. Os espectros de fosforescência dos complexos [Gd(BTC)(H2O)n] exibem uma banda larga característica da emissão de cor azul dos ligantes BTC3- (c.a. 450 nm); as medidas das energias dos estados tripleto T1 dos ligantes mostraram que as energias dos estados variam de 25100 a 25700 cm-1, energia que é superior às dos níveis emissores 5D0 e 5D4 dos íons Eu3+ e Tb3+, respectivamente. A eficiente transferência de energia ligante-TR3+ (TR3+ = Eu3+ e Tb3+) nos complexos é comprovada pelos seus espectros de excitação (a banda de excitação do ligante apresenta alta intensidade, com máximo em c.a. 295 nm) e de emissão (não apresentam a banda de fosforescência do ligante, mas sim as transições características dos íons TR3+). Os espectros de emissão dos complexos [Tb(BTC)(H2O)n] evidenciaram a intensa luminescência de cor verde destes complexos, especialmente do complexo anidro [Tb(TMA)], que apresenta a grande vantagem de não sofrer supressão de luminescência causada pelos níveis vibracionais intermediários da água. Os espectros de luminescência dos complexos [Eu(BTC)(H2O)n] apresentam bandas desdobradas em picos finos bem definidos, o que significa que os íons Eu3+ nos complexos se encontram em sítios de simetria bem definida, corroborando o caráter cristalino indicados pelos difratogramas de raios X. Dentre os complexos [TR(BTC)(H2O)n], os maiores tempos de vida dos estados emissores correspondem aos estados T1 dos ligantes BTC3- nos complexos com o íon Gd3+ (entre 7,386 e 12,025 ms), seguidos pelo nível 5D4 do íon Tb3+ (entre 0,712 e 1,265) e por fim pelo nível 5D0 do íon Eu3+ (entre 0,253 e 0,630). Os complexos [Eu(BTC)(H2O)n] ainda apresentaram valores de eficiência quântica entre 12 e 24% Este valor decresce com o aumento do número de moléculas de água do sistema, evidenciando o seu caráter supressor de luminescência. Os complexos [TR(BTC)(H2O)n] mostram-se promissores para serem aplicados como marcadores ópticos, camadas emissoras em dispositivos eletroluminescentes e no desenvolvimento de fluoroimunoensaios, devido: i) ao caráter monocromático das emissões dos complexos com Eu3+ e Tb3+; ii) à elevada intensidade luminescente dos complexos [Tb(BTC)(H2O)n]; e iii) às emissões nas três cores primárias apresentadas por estes complexos, dentre os quais os complexos de Eu3+ e Tb3+ se mostraram bons Dispositivos Moleculares Conversores de Luz (DMCLs) / This work reports the synthesis and characterization of Eu3+, Gd3+ and Tb3+ benzenetricarboxylate complexes and the correlation of their structural and chemical characteristics with their photoluminescent properties. The benzenetricarboxylate complexes [TR(BTC)(H2O)n] were prepared in aqueous solution, and were obtained in the form of white, insoluble and non-hygroscopic powders. The [TR(EMA)(H2O)2] complexes presents isomorphism among them as as the [TR(TLA)(H2O)4] complexes. The thermoanalysis curves showed that the [Eu(TMA)(H2O)6] and [Gd(TMA)(H2O)6] complexes have the same crystalline structure. However, the [Tb(TMA)] complex is anhydrous. The IR spectra of the [TR(BTC)(H2O)n] complexes confirm that the BTC3- ligands are coordinated to the TR3+ ions through the carboxylate groups. The phosphorescence spectra of [Gd(BTC)(H2O)n] complexes exhibit a broad and characteristic emission band of the BTC3- ligands (c.a. 450 nm); the mensure of the ligands T1 states indicated that the T1 state energies varies between 25100 and 25700 cm-1, which is highest than 5D0 and 5D4 states of Eu3+ and Tb3+ ions, respectively. The efficiency of the ligand-TR3+ energy transfer in the [Eu(BTC)(H2O)n] and [Tb(BTC)(H2O)n] complexes is confirmed by their spectra of excitation (high intensity of the ligand excitation band, c.a. 295 nm) and emission (they have no ligand phosphorescence band, but the characteristics emission bands of TR3+ ions). The emission spectra of the [Tb(BTC)(H2O)n] complexes exhibit their highly intense green luminescence, specially to the anhydrous [Tb(TMA)] complex, that present the advantage of not undergoing the luminescence suppression effect caused by coupling with the intermediary vibrational levels of the water molecules. The luminescence spectra of [Eu(BTC)(H2O)n] complexes presents non-degenerated emission bands in thin and well defined peaks, indicating that the Eu3+ ions are in chemical environment with well defined symmetry, confirming the crystalline character indicated by the X-rays diffractograms. The longest emission lifetimes (between 7,386 and 12,025 ms) of the [TR(BTC)(H2O)n] complexes were found with the Gd3+ complexes, followed by the Tb3+ complexes (0,712 to 1,265 ms), and the Eu3+ complexes (0,253 to 0,630 ms). The [Eu(BTC)(H2O)n] complexes presented quantum efficiencies between 12 and 24%. This value decreases with the growth of the hydration degree of the complex. The [TR(BTC)(H2O)n] complexes are promising candidates for applications such as optical markers, emission layers in electroluminescent devices and in the developing of fluoroimmunoassays due to: i) the monochromatic character of the Eu3+ and Tb3+ complexes emissions; ii) the high luminescence intensities of the [Tb(BTC)(H2O)n] complexes; and iii) the emissions in the three primary colors presented by this complexes. Moreover, the Eu3+ and Tb3+ complexes are efficient light conversion molecular devices (LCMDs)

Nenhuma / Este trabalho apresenta um estudo da separação dos elementos terras raras (ETR) cério (Ce) e térbio (Tb) através de técnicas hidrometalúrgicas. Para a realização do estudo, a INB Indústrias Nucleares do Brasil S.A., forneceu duas amostras; um licor sulfúrico proveniente do processamento da monazita contendo principalmente os ETR leves (La, Ce, Pr e Nd) e um carbonato dos ETR pesados contendo Tb, Dy, Ho, Er e Y também originado do processamento do licor da monazita. O estudo de separação do cério foi realizado em meio clorídrico. Para a preparação do licor clorídrico os ETR presentes no licor sulfúrico foram precipitados na forma de sulfato duplo de terras raras e sódio que foi convertido em hidróxido terras raras e então dissolvido em HCl. O estudo de obtenção do Ce de elevada pureza foi dividido em duas etapas: precipitação seletiva do cério e purificação do precipitado obtido. A separação do cério pela técnica investigada compreende dois fenômenos: a oxidação do Ce (III) a Ce (IV) e a precipitação Ce (IV) como hidróxido. Os oxidantes investigados foram: H2SO5, H2O2 e KMnO4. Devido ao fato do KMnO4 ser mais estável em meio básico, este foi utilizado em solução contendo Na2CO3 evitando assim sua degradação e auxiliando no controle do pH de precipitação do Ce(OH)4. Entre estes oxidantes, o KMnO4 se mostrou mais eficiente na oxidação do Ce. Após a escolha do agente oxidante, investigou-se as seguintes variáveis de processo: pH final, excesso de KMnO4, tempo de reação e razão molar KMnO4/Na2CO3. Os resultados indicaram a necessidade de um excesso de 30 % de KMnO4 para se ter a completa oxidação do Ce (III) a Ce (IV). Neste caso o Ce(OH)4 precipita juntamente com o MnO2. A purificação do cério foi realizada pela dissolução da mistura de dióxido de manganês e hidróxido de cério com solução de HCl e precipitação seletiva do cério mediante adição de solução de ácido oxálico ou de hidróxido de amônia. Ambos, ácido oxálico e hidróxido de amônia, mostraram-se eficientes na purificação do cério a partir da mistura de Ce/Mn. Após a purificação, os produtos obtidos apresentaram uma pureza entre 99 e 99,5 % de CeO2 com uma recuperação de cério superior a 98 %. A separação do térbio dos outros ETR pesados foi realizada usando a técnica de extração por solventes. Foram realizados experimentos descontínuos e contínuos. Nos experimentos descontínuos, investigou-se as seguintes variáveis de processo: tipo e concentração do agente extratante, acidez da fase aquosa, relação volumétrica entre as fases, tempo de contato e concentração do agente reextratante (solução de ácido clorídrico). Dez extratantes foram investigados: três ácidos organofosforados (DEHPA, IONQUEST801 e CYANEX272); uma mistura de DEHPA / TOPO (ester neutro), três extratantes quelantes (LIX63, LIX984N e LIX612N) e três extratantes básicos - aminas (ALAMINE336, ALIQUAT336 e PRIMENEJMT). Os extratantes organofosforados e extratantes quelantes foram investigados em meio clorídrico e sulfúrico, o desempenho das aminas foi avaliado em meio sulfúrico e a mistura de DEHPA / TOPO em meio clorídrico. Os melhores fatores de separação para os elementos adjacentes foram obtidos com DEHPA e IONQUEST801. Para DEHPA 1,0 mol L-1 em acidez inicial de 0,3 mol L-1 os fatores de separação foram: 2,5 Tb/Dy, 2,1 Dy/Ho, 1,9 Ho/Er, 2,0 Ho/Y e 1,1 Y/Er; para IONQUEST801 1,0 mol L-1 em 0,3 mol L-1 de H+ obteve-se 2,7 Tb/Dy, 2,4 Dy/Ho, 2,1 Ho/Er, 2,1 Ho/Y e 1,5 Y/Er. Os experimentos contínuos foram realizados em um circuito de misturadores decantadores composto das etapas de extração, lavagem, reextração e regeneração do solvente em sistema contracorrente utilizando IONQUEST801 como extratante. Dez experimentos contínuos foram conduzidos em 370 horas de operação, onde os ajustes pertinentes foram sendo realizados, até que a pureza e o rendimento desejados fossem alcançados. Após otimização das condições de processo, o circuito de extração por solventes foi constituído de 10 estágios na etapa de extração, 15 estágios na etapa de lavagem, 10 estágios na etapa de reextração e 2 estágios de regeneração do orgânico. No processo de separação do Tb apresentado, tanto o rendimento de separação como a pureza do produto obtido foram de aproximadamente 90 %. / This work presents a study of the separation of rare earth elements (REE) cerium (Ce) and terbium (Tb) through hydrometallurgic techniques. For the accomplishment of the study, the INB Indústrias Nucleares do Brasil S.A., supplied two samples: a sulphuric liquor from the monazite processing containing mainly the light REE (La, Ce, Pr and Nd) and a heavy REE carbonate containing Tb, Dy, Ho, Er and Y also obtained from the processing of the monazite liquor. The study of the separation of Ce was carried out in a hydrochloric medium. In order to prepare the hydrochloric liquor, the REE present in the sulfuric liquor were precipitated as sodium and RE double sulphate which was converted into RE hydroxide which was then dissolved in HCl. The study of the accomplishment of high purity cerium was divided into two steps: selective precipitation of cerium and the purification of the precipitated obtained. The separation of Ce through the technique investigated comprises two phenomena: oxidation of the Ce (III) into Ce (IV) and the precipitation of the Ce (IV) as hydroxide. The oxidant agents investigated were: H2SO5, H2O2 and KMnO4. Amongst these oxidants, KMnO4 presented the best results. After choosing the oxidant agent, the following process variables were investigated: final pH, KMnO4 excess, reaction time and the molar ratios of KMnO4 / Na2CO3. KMnO4 was used in a mixture with Na2CO3 in order to keep the stability of the solution. The results indicated that 30 % of KMnO4 excess was necessary to full oxidation of Ce (III) into Ce (IV). In such case Ce(OH)4 was precipitated together with MnO2. The cerium purification was carried out by dissolution of mixture of ceric hydroxide and manganese dioxide with HCl and it was then selectively precipitated through the addition of oxalic acid or an ammonium hydroxide solution. Both oxalic acid and ammonium hydroxide proved efficient in the precipitation of the cerium present in the mixture of Ce/Mn. After purification the final products assayed between 99 and 99.5 % of CeO2. The cerium recovery yield was greater than 98 %. The separation of terbium from other heavy REE was carried out through the solvent extraction technique. Non-continuous and continuous experiments were done. In the noncontinuous experiment, the following process variables were investigated: type and concentration of the extractants, acidity of the aqueous phase, aqueous / organic volumetric ratio, contact time and the stripping agent concentration (chloridric acid solution). Ten extractants were investigated: three organophosphorus acids (DEHPA, IONQUEST801 and CYANEX272), a mixture of DEHPA/TOPO (neutral ester), three chelating extractants (LIX63, LIX984N and LIX612N) and three basic extractants - amines (ALAMINE336, ALIQUAT336 and PRIMENEJM-T). The organophosphorus extractants and chelating extractants were investigated in hydrochloric and sulphuric media, the performance of the amines was assessed in a sulphuric medium and the mixture of DEHPA/TOPO in hydrochloric medium. The best separation factors for the adjacent elements were obtained with DEHPA and IONQUEST801. For 1 mol L-1 DEHPA in an initial acidity of 0.3 mol L-1, the separation factor was 2.5 Tb/Dy, 2.1 Dy/Ho, 1.9 Ho/Er, 2.0 Ho/Y and 1.1 Y/Er; for 1 mol L-1 IONQUEST801 in 0.3 mol L-1 of H+ it was 2.7 Tb/Dy, 2.4 Dy/Ho, 2.1 Ho/Er, 2.1 Ho/Y e 1.5 Y/Er. The continuous experiment was carried out in a mixer-settler circuit comprising extraction, scrubbing, stripping and solvent regeneration steps in a counter-current system using IONQUEST801 as extractant. Ten continuous experiments were conducted in 370 hours of operation having their variables continuously adjusted in consecutive runs until the desired yields and grades were achieved. The optimum operational circuit was composed of 10 stages in the extraction step, 15 stages in the scrubbing step, 10 stages in the striping step and 2 organic regeneration stages. A terbium product attaining 90 % purity with a yield of 90 % was obtained.Te

O presente trabalho aborda a síntese e caracterização de complexos benzenotricarboxilatos de íons Eu3+, Gd3+ e Tb3+, com o intuito de investigar suas características químicas e estruturais e correlacioná-las com as propriedades fotoluminescentes. Os complexos benzenotricarboxilato [TR(BTC)(H2O)n] foram sintetizados em solução aquosa, e apresentaram-se na forma de pós brancos, não-higroscópicos e insolúveis em solventes polares ou apolares. Os complexos com o ligante EMA se mostraram isomórficos e com grau de hidratação igual a dois. Os complexos com o ligante TLA também apresentaram isomorfismo, mas com estrutura cristalina diferente da dos complexos com os outros ligantes. Os complexos [Eu(TMA)(H2O)6] e [Gd(TMA)(H2O)6] apresentaram a mesma estrutura cristalina; entretanto, o complexo [Tb(TMA)] se mostrou anidro, o que foi confirmado pela termoanálise. Os espectros de absorção na região do invravermelho dos complexos evidenciaram que os ligantes BTC3- se coordenam aos íons TR3+ através dos grupos carboxilato desprotonados. Os espectros de fosforescência dos complexos [Gd(BTC)(H2O)n] exibem uma banda larga característica da emissão de cor azul dos ligantes BTC3- (c.a. 450 nm); as medidas das energias dos estados tripleto T1 dos ligantes mostraram que as energias dos estados variam de 25100 a 25700 cm-1, energia que é superior às dos níveis emissores 5D0 e 5D4 dos íons Eu3+ e Tb3+, respectivamente. A eficiente transferência de energia ligante-TR3+ (TR3+ = Eu3+ e Tb3+) nos complexos é comprovada pelos seus espectros de excitação (a banda de excitação do ligante apresenta alta intensidade, com máximo em c.a. 295 nm) e de emissão (não apresentam a banda de fosforescência do ligante, mas sim as transições características dos íons TR3+). Os espectros de emissão dos complexos [Tb(BTC)(H2O)n] evidenciaram a intensa luminescência de cor verde destes complexos, especialmente do complexo anidro [Tb(TMA)], que apresenta a grande vantagem de não sofrer supressão de luminescência causada pelos níveis vibracionais intermediários da água. Os espectros de luminescência dos complexos [Eu(BTC)(H2O)n] apresentam bandas desdobradas em picos finos bem definidos, o que significa que os íons Eu3+ nos complexos se encontram em sítios de simetria bem definida, corroborando o caráter cristalino indicados pelos difratogramas de raios X. Dentre os complexos [TR(BTC)(H2O)n], os maiores tempos de vida dos estados emissores correspondem aos estados T1 dos ligantes BTC3- nos complexos com o íon Gd3+ (entre 7,386 e 12,025 ms), seguidos pelo nível 5D4 do íon Tb3+ (entre 0,712 e 1,265) e por fim pelo nível 5D0 do íon Eu3+ (entre 0,253 e 0,630). Os complexos [Eu(BTC)(H2O)n] ainda apresentaram valores de eficiência quântica entre 12 e 24% Este valor decresce com o aumento do número de moléculas de água do sistema, evidenciando o seu caráter supressor de luminescência. Os complexos [TR(BTC)(H2O)n] mostram-se promissores para serem aplicados como marcadores ópticos, camadas emissoras em dispositivos eletroluminescentes e no desenvolvimento de fluoroimunoensaios, devido: i) ao caráter monocromático das emissões dos complexos com Eu3+ e Tb3+; ii) à elevada intensidade luminescente dos complexos [Tb(BTC)(H2O)n]; e iii) às emissões nas três cores primárias apresentadas por estes complexos, dentre os quais os complexos de Eu3+ e Tb3+ se mostraram bons Dispositivos Moleculares Conversores de Luz (DMCLs) / This work reports the synthesis and characterization of Eu3+, Gd3+ and Tb3+ benzenetricarboxylate complexes and the correlation of their structural and chemical characteristics with their photoluminescent properties. The benzenetricarboxylate complexes [TR(BTC)(H2O)n] were prepared in aqueous solution, and were obtained in the form of white, insoluble and non-hygroscopic powders. The [TR(EMA)(H2O)2] complexes presents isomorphism among them as as the [TR(TLA)(H2O)4] complexes. The thermoanalysis curves showed that the [Eu(TMA)(H2O)6] and [Gd(TMA)(H2O)6] complexes have the same crystalline structure. However, the [Tb(TMA)] complex is anhydrous. The IR spectra of the [TR(BTC)(H2O)n] complexes confirm that the BTC3- ligands are coordinated to the TR3+ ions through the carboxylate groups. The phosphorescence spectra of [Gd(BTC)(H2O)n] complexes exhibit a broad and characteristic emission band of the BTC3- ligands (c.a. 450 nm); the mensure of the ligands T1 states indicated that the T1 state energies varies between 25100 and 25700 cm-1, which is highest than 5D0 and 5D4 states of Eu3+ and Tb3+ ions, respectively. The efficiency of the ligand-TR3+ energy transfer in the [Eu(BTC)(H2O)n] and [Tb(BTC)(H2O)n] complexes is confirmed by their spectra of excitation (high intensity of the ligand excitation band, c.a. 295 nm) and emission (they have no ligand phosphorescence band, but the characteristics emission bands of TR3+ ions). The emission spectra of the [Tb(BTC)(H2O)n] complexes exhibit their highly intense green luminescence, specially to the anhydrous [Tb(TMA)] complex, that present the advantage of not undergoing the luminescence suppression effect caused by coupling with the intermediary vibrational levels of the water molecules. The luminescence spectra of [Eu(BTC)(H2O)n] complexes presents non-degenerated emission bands in thin and well defined peaks, indicating that the Eu3+ ions are in chemical environment with well defined symmetry, confirming the crystalline character indicated by the X-rays diffractograms. The longest emission lifetimes (between 7,386 and 12,025 ms) of the [TR(BTC)(H2O)n] complexes were found with the Gd3+ complexes, followed by the Tb3+ complexes (0,712 to 1,265 ms), and the Eu3+ complexes (0,253 to 0,630 ms). The [Eu(BTC)(H2O)n] complexes presented quantum efficiencies between 12 and 24%. This value decreases with the growth of the hydration degree of the complex. The [TR(BTC)(H2O)n] complexes are promising candidates for applications such as optical markers, emission layers in electroluminescent devices and in the developing of fluoroimmunoassays due to: i) the monochromatic character of the Eu3+ and Tb3+ complexes emissions; ii) the high luminescence intensities of the [Tb(BTC)(H2O)n] complexes; and iii) the emissions in the three primary colors presented by this complexes. Moreover, the Eu3+ and Tb3+ complexes are efficient light conversion molecular devices (LCMDs)

Les complexes luminescents de lanthanides font l'objet d'une recherche importante dans le domaine de l'opto-électronique du fait de couleur pure et de rendements quantiques importants. Le développement de nouveaux chelates spécifiquement adaptés pour des applications opto-électroniques reste cependant un domaine moins développé par rapport à d'autres applications.<br /><br />Le but de ce travail est d'accéder à de nouvelles possibilités de synthèse dans le domaine des émetteurs moléculaires à base de lanthanides pour l'opto-electronique ; ceci, en concevant de nouveaux ligands adaptés à la complexation de ces métaux et l'étude des propriétés optiques des complexes formés.<br /><br />A cette fin nous avons synthétisés et étudiés une série de ligands basés sur des motifs terpyridine-, bipyridine- et pyridine-tetrazole. Divers substituants ont été ajoutés afin de moduler les propriétés électroniques de ces molécules avec, pour résultats, l'obtention de fortes efficacités lumineuses pour certains de ces complexes tant dans le visible que le proche infrarouge. Les effets induits par l'ajout des divers subtituants sur leurs propriétés photophysiques ont été clairement démontré. De plus, nous avons également synthétisés et testé en couche active de dispositifs OLED une nouvelle classe de complexes neutres complétées par des unités dicétonates.<br /><br />Nous avons par ailleurs explorés la sensibilisation des ions lanthanides par l'intermédiaire de complexes de métaux de transition d. Pour cela nous avons conçus une nouvelle architecture hétéro-métallique d-f où le complexe d'iridium est employé comme antenne. Finalement, nous avons étudiés les processus de transfert d'énergie par mesures de luminescence.

Lanthanum orthoborate (LaBO3) has aroused interest of scientists for many decades because of their remarkable properties and potential applications. They provide favorable magnetic properties for various applications. Additionally, they possess high VUV transparency and exceptional optical damage when they compose with rare earth elements. This study comprises the synthesis of pure lanthanum orthoborate, europium, dysprosium and terbium doped lanthanum orthoborate by two methods with v three fuels, citric acid, glycine and urea. LaBO3 has already been synthesized by various methods, however / in this work, two alternative roads are suggested, microwave assisted method and sol-gel microwave assisted method. The second task of the work is to find out the best luminescent product by altering the synthesis conditions, type of the doping material and the doping amount of the rare earth element. For the microwave assisted combustion method, urea was used as a fuel. After synthesis in the microwave oven, further heating up to 950&deg / C was performed. For the microwave assisted sol-gel method, citric acid and glycine were used. After obtaining the gel mixture, the product is synthesized in the microwave oven at 1200 W for ten minutes. For this route, again 950&deg / C heating for 2 hours was performed. Powder X-ray diffraction method was employed for the characterization of the material. The morphological properties of doped and un-doped materials were studied by SEM (Scanning Electron Microscope) and TEM (Transmission Electron Microscope). Besides, FT-IR (Fourier Transform Infra red) spectrometry analyses were performed to detect the differences in the bond structure and also to identify the corresponding bands. Luminescence studies were performed to detect the best emission intensities by using Fluorescence spectroscopy. The XRD patterns confirmed that lanthanum orthoborate production was successful by three precursors. The space group is Pnma, and the crystal system is orthorhombic with the unit cell dimensions / a= 5.8761(1)

The development and application of advanced materials is a very important task of today's information society. Garnet crystal structure compounds because of their specific physical and chemical properties are widely used in information technology, manufacturing of solid-state lasers and optical equipments, medical equipments and many other areas. Therefore, these materials because of their unique properties and characteristics are of high interest so far. For the first time Ce-Al-O, Pr-Al-O, Nd-Al-O, Tb-Al-O, Dy-Al-O, Ho-Al-O, Er-Al-O, Tm-Al-O, Yb-Al-O, Lu-Al-O, Y(Nd)-Al-O and Y(Sm)-Al-O acetate-nitrate-glycolate gels have been synthesized using environmentally friendly, economical and simple aqueous sol-gel method. They were used as starting materials for the synthesis of appropriate lanthanide aluminium garnets. The results of X-ray difraction analysis have indicated that single-phase terbium aluminium garnet (Tb3Al5O12), dysprosium aluminium garnet (Dy3Al5O12), holmium aluminium garnet (Ho3Al5O12), erbium aluminium garnet (Er3Al5O12), thulium aluminium garnet (Tm3Al5O12), ytterbium aluminium garnet (Yb3Al5O12) and lutetium aluminium garnet (Lu3Al5O12) have been synthesized by annealing Tb-Al-O, Dy-Al-O, Ho-Al-O, Er-Al-O, Tm-Al-O, Yb-Al-O and Lu-Al-O precursor gels for 10 hours at 1000 °C, respectively. For the first time these garnet structure compounds were synthesized using sol-gel method. Moreover, these lanthanide aluminium garnets were synthesized at relatively low... [to full text] / Pažangių medžiagų bei technologijų kūrimas ir taikymas - tai labai svarbus šiandieninės informacinės visuomenės uždavinys. Granato kristalinės struktūros medžiagos, pasižymėdamos ypatingomis fizikinėmis bei cheminėmis savybėmis, yra plačiai naudojamos informacinių technologijų, kietafazių lazerių, optikos įrenginių gamybose, medicinos įrangose, bei daugelyje kitų sričių. Todėl jos dėl savo unikalių savybių ir plačiai tebetyrinėjamos iki šiol. Šiame darbe pirmą kartą buvo susintetinti Ce-Al-O, Pr-Al-O, Nd-Al-O, Tb-Al-O, Dy-Al-O, Ho-Al-O, Er-Al-O, Tm-Al-O, Yb-Al-O, Lu-Al-O, Y(Nd)-Al-O ir Y(Sm)-Al-O acetatiniai-nitratiniai-glikoliatiniai geliai zolių-gelių metodu vandeniniuose tirpaluose. Jie buvo panaudoti pradinėmis medžiagomis atitinkamų lantanoidų aliuminio granatų sintezei. Vienfaziai terbio aliuminio granatas (Tb3Al5O12), disprozio aliuminio granatas (Dy3Al5O12), holmio aliuminio granatas (Ho3Al5O12), erbio aliuminio granatas (Er3Al5O12), tulio aliuminio granatas (Tm3Al5O12), iterbio aliuminio granatas (Yb3Al5O12) ir liutecio aliuminio granatas (Lu3Al5O12) buvo gauti, terbio jonų šaltiniu naudojant terbio oksidą, disprozio – disprozio oksidą, holmio – holmio oksidą, erbio – erbio oksidą, tulio – tulio oksidą, iterbio – iterbio oksidą, lutecio – liutecio oksidą, kompleksus sudarančiu reagentu 1,2-etandiolį. Tyrimų rezultatai parodė, kad šių lantanoidų aliuminio granatai gauti santykinai žemoje temperatūroje (1000°C). Zolių-gelių metodu sintetinant cerio aliuminio granatą... [toliau žr. visą tekstą]