La possibilité d’obtenir une émission laser efficace sur une large bande spectrale autour de 1.05 µm a été démontrée récemment en utilisant des monocristaux CaF2 and SrF2 dopés Nd3+. Cette émission, éteinte du fait de la relaxation croisée entre ions dans les matériaux de type fluorite, peut être exaltée avec l’insertion d’ions “tampons” comme Y3+ ou Lu3+. Une émission laser accordable sur une large bande spectrale et la génération d’impulsions ultracourtes sont donc possibles. De plus, ce type de matériau est particulièrement intéressant pour des amplificateurs de forte puissance pompés par diodes. Une étude complète des propriétés spectrales et thermomécaniques de cristaux de CaF2:Nd3+ co-dopés avec des concentrations variables de Lu3+ a été menée en collaboration avec le CEA CESTA au sein du projet LASCAN pour de futurs développements au sein du Laser MégaJoule (LMJ) avec pour but l’amélioration des performances des amplificateurs pilotes. L’effet d’élimination des clusters de Nd3+ par le co-dopage avec le Lu3+ et l’apparition de deux sites actifs différents a été mise en évidence et caractérisée en détail. Ce travail présente ainsi une spectroscopie complète des centres actifs dans CaF2:Nd3+,Lu3+, une étude des propriétés thermomécaniques, ainsi que des propriétés d’amplification optique des matériaux étudiés. / It was recently demonstrated that efficient and broadband laser emission was possible with Nd-doped CaF2 and SrF2 single crystals around 1.05 µm. Such laser emission, known as completely quenched because of cross-relaxation in the singly doped fluorites, increases spectacularly by co-doping with non-optically active “buffer” ions like Y3+ or Lu3+. Broadband laser emission and ultra-short laser operation are therefore possible. The material is particularly appealing for large scale high peak power diode-pumped amplifiers. A deep investigation of the spectral properties of CaF2:Nd3+ crystals co-doped with various amounts of Lu3+ was performed. The cluster breaking effect of Lu3+ codoping has as a side-effect the appearance of two different contributions, identified as two different active sites, which is in agreement with recent observations. In this work, we investigate in depth the different centres’ spectroscopic properties and operational parameters for laser applications,their evolution as the lutetium concentration increases, and the thermomechanical properties of said samples. A preliminary investigation on the amplification properties and laser operation of said materials is performed as well.

The Paris Agreement aims to limit the global temperature to below 2°C above the pre-industrial level. In order to achieve this target, almost 200 countries committed to Nationally Determined Contributions to reduce their greenhouse gas emissions. Diverse strategies are applied to achieve the necessary emissions reductions. One such strategy is large-scale renewable energy deployment. Certain key minerals are needed to produce green technologies such as electric vehicles and wind turbines. This thesis is concerned with the minerals cobalt, lithium and rare earths which are key components of lithium-ion batteries and/or permanent magnets used in many green technology applications. The academic community is aware that these critical materials are largely found in fragile and undemocratic states. The question is how the energy transition may be impacted by the fragile state of critical mineral producing countries. Therefore, this thesis aimed to investigate the supply and geopolitical risks on the critical materials market in the short- and medium-term. An analysis of the markets and a projection of their future development were conducted through maximum depletion rate modelling, the calculation Herfindahl-Hirschman indexes and risk-weighting country index scores. The results showed that the mineral markets are projected to remain highly concentrated which points to a continued vulnerability to risks emanating from individual production countries. The study found that the kinds of risk categories impacting a market depend on the distribution of market shares among countries. As production constraints arise in individual countries, the risk portfolio of the market changes. The study also concluded that countries like China that invest in mining projects abroad can contribute to the risks of a mineral that they are not producing themselves.

[pt] Neste trabalho são reportados o preparo, a caracterização e os estudos de luminescência de filmes do polímero 1,7-polioxepan-2-ona (policaprolactona, PCL) dopados com complexos trisacetilacetonatos (acac) de Terras Raras trivalentes (TR igual a Eu3 positivo, Gd3 positivo e Tb3 positivo). Os dados de microanálise de CHN evidenciaram que a fórmula geral para os compostos precursores é (TR(acac)3(H2O)3). Os espectros de absorção na região do infravermelho (FTIR) e os espectros Raman indicaram que a coordenação dos ligantes B-dicetonas aos íons TR3 positivo ocorre através dos átomos de oxigênio dos grupos carbonila. Os filmes de PCL foram dopados com (TR(acac)3(H2O)3) em concentrações de 1, 5, 10, 15 e 20 porcento (m/m). Os dados de FTIR e Raman evidenciaram a interação entre o polímero PCL e os B-dicetonatos de TR. As análises termogravimétricas indicaram o caráter anidro das matrizes poliméricas dopadas e melhoria da estabilidade térmica comparados aos complexos precursores. Os espectros de emissão dos sistemas PCL:Eu e PCL:Tb apresentam bandas finas características das transições intraconfiguracionais dos íons Eu3 positivo (5D0-7F0-4) e Tb3 positivo (5D4-7F6-0) que exibem as cores vermelha e verde, respectivamente. Além de supressão de luminescência por concentração, também foram observadas perdas de intensidade da emissão dos filmes ao longo do tempo. Os filmes dopados com Eu3 positivo apresentam maiores tempos de vida do nível emissor 5D0 e eficiências quânticas, indicando que o PCL participa no processo de transferência de energia ligante-metal e co-sensibiliza os íons TR3 positivo. / [en] In this work we report the preparation, characterization and the luminescence studies 1,7-polyoxepan-2-one (polycaprolactone, PCL) polymer films doped with trivalent Rare Earth (RE = Eu3 positive, Gd3 positive e Tb3 positive) trisacetylacetonate (acac) complexes. The CHN microanalysis data confirmed that the general formula for the precursor compounds is (RE(acac)3(H2O)3). The absorption spectra in the infrared region (FTIR) and Raman spectra indicated that the coordination of the B-diketone ligands to RE3 positive ions occurs through the oxygen atoms of carbonyl groups. The PCL films were doped with (RE(acac)3(H2O)3) at concentrations of 1, 5, 10, 15 and 20 porcento (w/w). FTIR and Raman data demonstrated the interaction between PCL polymer and rare earth B-diketonates. The thermogravimetric analysis indicated the anhydrous character of the doped polymer matrices and improvement of thermal stability, in comparison with the precursor complexes. The emission spectra of the PCL:Eu and PCL:Tb systems present characteristic narrow bands of the intraconfigurational transitions of Eu3 positive (5D0-7F0-4) and Tb3 positive (5D4-7F6-0), exhibiting red and green colors, respectively. In addition to concentration quenching of luminescence, losses of emission intensities were also observed over time. The Eu3 positive-doped films exhibit higher lifetimes of the 5D0 emitting level and quantum efficiencies, indicating that the PCL participates in the ligand–metal energy transfer process and co-sensitizes the RE3 positive ions.

No description available.

Atmospheres play an important role in the habitability of a planet, so understanding and modelling them is an important step in the search for life on other planets. This thesis presents a 1D frequency-dependent radiative-convective code that was written to help determine the temperature-pressure structure of potentially-habitable exoplanets. This code pairs with a chemistry model to determine the chemical composition of these planets' atmospheres. This code is applied to the planets in the TRAPPIST-1 system. The initial atmospheric compositions of the TRAPPIST-1 planets are determined through planet formation history and considered for both outgassed and accreted atmospheres. An interesting result is found when running these initial atmospheric compositions through the chemistry model: when the atmosphere equilibrates, it can change its C/O ratio from equal to that found in the accreted or outgassed volatiles to something lower, because, in temperate conditions, CO$_2$ is favoured over CO. This has the consequence that observed C/O ratios in terrestrial atmospheres cannot be relied on to infer the C/O ratio of the protoplanetary disc in which the planet formed. The initial results of atmospheric modelling for TRAPPIST-1 planets indicate that these planets are likely to have relatively warmer upper atmospheres due to the fact that their host star emits primarily in the infrared, and a portion of this radiation is then absorbed as it enters the top of the atmosphere. These initial results have not been seen in previous work. These initial results are the beginning of a database of potential atmospheres on the TRAPPIST-1 planets. It is hoped that these atmospheres can be compared with observations from future observing missions like the James Webb Space Telescope to help constrain the surface conditions of these potentially-habitable planets and ultimately, to help in the search for life. / Thesis / Master of Science (MSc)

No / Two new complexes, [Fe3(μ3-O)(inicH)6(H2O)3][Gd(NO3)6]·(NO3)4·nH2O (1) and [Fe3(μ3-O)(inicH)6(H2O)3][Dy(NO3)5 (H2O)]·(NO3)5·n(H2O) (2) with two isolated complex moieties, were generated when isonicotinic acid was treated with iron(III) nitrate and the corresponding lanthanide(III) nitrate in water. The structures were determined by single-crystal X-ray diffraction studies. In these compounds, the anionic lanthanide complexes are encapsulated by trinuclear [Fe3(μ3-O)(inicH)6(H2O)3]7+ cationic cluster units, which is facilitated by hydrogen-bonding interactions. Investigation of the magnetic properties reveals that 2 shows slow relaxation of magnetization at low magnetic field (Hdc = 1.0 kOe), with an energy barrier of 23 K originating from a single [Dy(NO3)5(H2O)]2– anion. / Errata: 2014(25): 4228 (http://onlinelibrary.wiley.com/enhanced/doi/10.1002/ejic.201402684)

No / This article corrects http://onlinelibrary.wiley.com/enhanced/doi/10.1002/ejic.201402114. 2014(19): 3065-3071.

Luminóforos inorgânicos contendo Terras Raras (TR) apresentam um papel importante como detectores de radiação ionizante, aplicados em diagnósticos médicos por imagem, como radiologia e tomografia. A função dos luminóforos é transformar os fótons da radiação de alta energia absorvidos (raios X ou ?) em fótons de luz visível, promovendo melhor qualidade de imagem e, conseqüentemente menor tempo de exposição do paciente à radiação. Os luminóforos de TR consistem de uma matriz hospedeira onde estão presentes íons de TR como Lu, La, Y ou Gd e de um íon ativador (que emite luz na região visível do espectro) como Eu3+, Tb3+, Tm3+ ou Ce3+, por exemplo. Luminóforos contendo íons Ce3+ como ativador são alvo de várias pesquisas relacionadas com detecção de radiação ionizante, devido às rápidas transições 5 d ? 4 f (tempo de resposta de ~ 10 a 100 ns) e emissão de luz na região do azul ou verde, requisitos esperados para um eficiente luminóforo para tal aplicação. Este trabalho apresenta a preparação de luminóforos de TR, dopados com Ce3+ ou Tm3+, na forma de pó, por diferentes métodos de síntese, como os métodos de combustão e Pechini e também por processo sol-gel. Aluminatos de TR (Lu3Al5O12 e Y3Al5O12) dopados com cério ou túlio foram obtidos pela reação de combustão entre precursores nitrato com uréia ou glicina sob aquecimento, ou pela síntese de polímeros de ácido cítrico com etilenoglicol contendo íons TR e alumínio (método Pechini). Em ambos os métodos os compostos foram obtidos por calcinação a temperaturas baixas quando comparadas às dos métodos convencionais. Silicatos de TR (Gd2SiO5, Lu2SiO5 e Y2SiO5) dopados com cério ou túlio foram preparados pelo método sol-gel convencional, por reação entre tetraetóxisilano (TEOS), etanol, água e nitratos metálicos, sob catálise básica, e por um método sol-gel modificado utilizando um polímero precursor. Neste último procedimento, TEOS, etanol e água reagiram juntamente com um sal orgânico de TR, álcool polivinílico (PVA) e uréia como combustível, produzindo um gel. Posterior calcinação levou à formação do silicato. A caracterização dos compostos foi realizada por análises de difratometria de raios X pelo método do pó (DRX), microscopia de eletrônica de varredura (MEV) ou de transmissão (MET), EDX, excitação e emissão no UV-Vis e tempo de vida de luminescência. Para os aluminatos dopados com cério foram ainda realizados espectros de emissão sob excitação por raios X. Os métodos de síntese utilizados se mostraram eficientes para obtenção de luminóforos na forma de pó nanométrico, com exceção do método sol-gel modificado, pois para algumas amostras observou-se a formação de mistura de fases. Os compostos dopados com cério apresentaram excitação e emissão características desse íon na região do verde ou azul do espectro visível, dependendo da matriz, com tempos de vida menores que 100 ns. Já aqueles dopados com túlio apresentaram emissão característica do íon, na região do azul, porém com tempos de vida da ordem de microssegundos. / Rare Earth (RE) inorganic phosphors play an important role as ionizing radiation detectors when applied to medical imaging techniques like radiology and tomography. These phosphors is to convert the high energy radiation absorbed photons (X or ?-rays) into visible photons, leading to better quality images and reducing the time the patient is exposed to radiation. RE phosphors consist of a host lattice where RE ions such as Lu, La, Y, or Gd are present, as well as activator ions (which emit light in the visible range of the spectrum) such as Eu3+, Tb3+, Tm3+, or Ce3+. Cerium-doped phosphors have been the target of several researches related with ionizing radiation detection due to their 5d - 4 f fast transitions (decay time in the ~ 10 to 100 ns range) and due to the fact that they emit light in the blue or green region of the spectrum, which is required for to the efficient phosphors to be applied in the detection of X or ?-rays. This work presents the synthesis of RE phosphor powders doped with Ce3+ or Tm3+, through different synthetic methods: combustion, Pechini, and sol-gel. RE aluminates (Lu3Al5O12 and Y3Al5O12) doped with Ce or Tm were prepared by combustion reaction between nitrate precursors and urea or glycine under heating. They were also obtained via the synthesis of polymers using citric acid, ethileneglycol, RE3+ and Al3+ ions (Pechini method). In both cases, the compounds were obtained by calcination at lower temperatures than those used inconventional methods. RE silicates (Gd2SiO5, Lu2SiO5 e Y2SiO5) doped with Ce or Tm were synthesized by the conventional sol-gel method using tetraethoxisylane (TEOS), ethanol and water, under basic catalysis, and also by a modified sol-gel route that uses a polymeric precursor. In the latter one, TEOS, ethanol and water were reacted with an organic RE salt, polyvinyl alcohol (PVA), and urea was used as fuel, thus yielding a gel. After calcination, we observed silicate formation. Characterization of the compounds was performed by X-ray diffractometry (XRD ? powder method), scanning or transmission electron microscopy (SEM or TEM), energy dispersive X-ray (EDX), luminescence spectroscopy in the UV-Vis range and lifetime analyses. For the cerium doped aluminates, emission spectra under X-ray excitation were also obtained. The synthetic methods used here showed to be efficient for the preparation of nanometric phosphor powders except for the modified sol-gel route, because in this case formation of a mixture of phases was observed for some samples. The Ce-doped compounds exhibited excitation and emission features of this ion in either the green or blue region of the visible spectrum, depending on the matrix, with lifetime values lower than 100 ns. However, the Tm-doped compounds displayed the blue emission typical of Tm ions, but the lifetime values were in the range of microseconds.

This study investigates the photoluminescence (PL), cathodoluminescence (CL), radioluminescence (RL) and ionoluminescence (IL) of natural and synthetic minerals. The natural minerals (fluorapatite, leucophanite, meliphanite and zircon) are mostly from Ilímaussaq Alkaline Complex in South Greenland, Langesundsfjord in Norway and from different localities within Scotland. Synthetic fluorapatite (manufactured as part of the present study) and zircon doped with rare earth elements (REE) were used to compare single and multidoped materials. This study has shown that many of the generally accepted applications of luminescence are not as straightforward as often suggested by the current literature. For example, the study demonstrates how site distribution of REE, based on luminescence, is greatly affected by the dopant level and structural changes, and that different conclusions can be drawn on the same sample depending on method applied. Furthermore, it is clearly demonstrated that using luminescence as a tool for quantitative trace element determination is not going to be a standard technique in the near future if ever. The two main findings supporting this conclusion are the non-linear intensity decrease between different REE activators in the same sample and a large variation between activators at the concentration at which self-quenching starts. In contrast to the general perception that luminescence related to REE is mostly independent of the host, this study has shown a strong interaction between host and REE activators. This conclusion is supported by the change in the activator’s coordination polyhedron observed with single-crystal and powder X-ray diffraction combined with full chemical characterisation. When combining the weak interaction between some REE with the strong host interaction this study has shown the potential for designing new types of colour tuneable and “white light” LEDs based on natural minerals. This study also reveals that zircon doped with Gd³⁺ and Eu³⁺ can potentially have quantum-cutting properties.

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)