Dissertations / Theses: 'Rare earth ion dopants'

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Longdell, Jevon Joseph, and jevon longdell@anu edu au. "Quantum Information Processing in Rare Earth Ion Doped Insulators." The Australian National University. Research School of Physical Sciences and Engineering, 2004. http://thesis.anu.edu.au./public/adt-ANU20061010.105020.

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A great deal of theoretical activity has resulted from blending the fields of computer science and quantum mechanics. Out of this work has come the concept of a quantum computer, which promises to solve problems currently intractable for classical computers. This promise has, in turn, generated a large amount of effort directed toward investigating quantum computing experimentally. ¶ Quantum computing is difficult because fragile quantum superposition states of the computers register must be protected from the environment. This is made more difficult by the need to manipulate and measure these states. ¶ This thesis describes work that was carried out both to investigate and to demonstrate the utility of rare earth ion dopants for quantum computation. Dopants in solids are seen by many as a potential means of achieving scalable quantum computing. Rare earth ion dopants are an obvious choice for investigating such quantum computation. Long coherence times for both optical and nuclear spin transitions have been observed as well as optical manipulation of the spin states. The advantage that the scheme developed here has over nearly all of its competitors is that no complex nanofabrication is required. The advantages of avoiding nano-fabrication are two fold. Firstly, coherence times are likely to be adversely effected by the damage to the crystal structure that this manufacture represents. Secondly, the nano-fabrication presents a very serious difficulty in itself. ¶ Because of these advantages it was possible to perform two-qubit operations between independent qubits. This is the first time that such operations have been performed and presents a milestone in quantum computation using dopants in solids. It is only the second time two-qubit operations have been demonstrated in a solid. ¶ The experiments performed in this thesis were in two main areas: The first was the characterisation of hyperfine interactions in rare earth ion dopants; the second, simple demonstrations directly related to quantum computation. ¶ The first experiments that were carried out were to characterise the hyperfine interactions in Pr[superscript 3]+:Y[subscript 2]SiO[subscript 5]. The characterisation was the first carried out for the dopants in a site of such low symmetry. The resulting information about oscillator strengths and transition frequencies should prove indispensable when using such a system for quantum computation. It has already enabled an increase in the coherence times of nuclear spin transitions by two orders of magnitudes. ¶ The experiments directly related to the demonstration of quantum computation were all carried out using ensembles. The presence of a significant distribution of resonant frequencies, or inhomogeneous broadening, meant that many different sub-ensembles could be addressed, based on their resonant frequencies. Furthermore, the properties of the sub-ensembles could be engineered by optically pumping unwanted members to different hyperfine states away from resonance with the laser. ¶ A previously demonstrated technique for realising ensembles that could be used as single qubits was investigated and improved. Also, experiments were carried out to demonstrate the resulting ensembles utility as qubits. Further to this, ions from one of the ensembles were selected out, based on their interaction with the ions of another. Elementary two qubit operations were then demonstrated using these ensembles.

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Zhen, Y. S. "Oxygen ion conduction in doped rare earth oxides." Thesis, University of Leeds, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.383333.

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Shen, Shaoxiong. "New rare earth ion-doped hosts for broadband fibre amplifier." Thesis, University of Leeds, 2000. http://etheses.whiterose.ac.uk/2379/.

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Three kinds of oxide glasses doped with Er3+ ions were chosen for investigation. Both the properties of glass and fluorescence from rare earth dopant ions are measured and discussed. In Er3+ ion doped silicate glass, the changes in the structure of glass as a result of fluorine addition are studied by measuring the glass properties: density, molar volume, refractive index, IR and UV edges. The absorption and emission cross- sections of Er3+ ion increase with increasing value of F/O ratio as do the full width of half maximum (FWHM) and figure-of-merit (FOM) for gain and bandwidth. In Er3+ ion doped heavy metal germanate glass, the structural units of forming network in germanate glass change with the addition of PbO, Bi2C>3, Ga2C>3 and TeC>2. The molar volume, glass transition temperature Tg, IR and UV edges have been measured and discussed with the relation of glass structure. More Er3+ ion sites result in the increase of absorption and emission cross-sections, emission FWHM and FOM for gain. In Er3+ doped Te02 - ZnO - R2O (R2O = Li20, Na20 and K2O) tellurite glass system, glass properties such as density, molar volume, transition temperature Tg, IR and UV edges are measured and discussed. The glass structure has been characterised using Raman spectra. The role of F' and Cl' has also been studied in tellurite glass. Crystallisation kinetics has been analysed in tellurite glass using isothermal and non- isothermal methods. The properties of Er3+ absorption and emission have been measured and discussed with the change of glass structure and concentrations. FOM for gain and bandwidth have also been compared and discussed in Er3+ doped modifies silicate, HMO germanate, tellurite and ZBLAN fluoride glasses. The tellurite glass fibre has been made and the emission spectra of Er3+ ion in fibre have been measured. Absorption and emission spectra have been studied in Tm -doped tellurite glass, it shows to be a highly promising host for a 1.47 (im amplifier capable of providing extended short-wavelength gain and a continuous band with the tellurite EDFA. Nd3+- doped tellurite and silicate glasses have also been studied, amplifier operating around 1.34 (j.m is clearly desirable in tellurite glass. A continuous gain band extending from 1310 to 1600 nm may become possible by using Nd3+, Tm3+ and Er3+ amplifiers.

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Fraval, Elliot, and elliot fraval@gmail com. "Minimising the Decoherence of Rare Earth Ion Solid State Spin Qubits." The Australian National University. Research School of Physical Sciences and Engineering, 2006. http://thesis.anu.edu.au./public/adt-ANU20061010.124211.

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[Mathematical symbols can be only approximated here. For the correct display see the Abstract in the PDF files linked below] This work has demonstrated that hyperfine decoherence times sufficiently long for QIP and quantum optics applications are achievable in rare earth ion centres. Prior to this work there were several QIP proposals using rare earth hyperfine states for long term coherent storage of optical interactions [1, 2, 3]. The very long T_1 (~weeks [4]) observed for rare-earth hyperfine transitions appears promising but hyperfine T_2s were only a few ms, comparable to rare earth optical transitions and therefore the usefulness of such proposals was doubtful. ¶ This work demonstrated an increase in hyperfine T_2 by a factor of 7 × 10^4 compared to the previously reported hyperfine T_2 for Pr^[3+]:Y_2SiO_5 through the application of static and dynamic magnetic field techniques. This increase in T_2 makes previous QIP proposals useful and provides the first solid state optically active Lamda system with very long hyperfine T_2 for quantum optics applications. ¶ The first technique employed the conventional wisdom of applying a small static magnetic field to minimise the superhyperfine interaction [5, 6, 7], as studied in chapter 4. This resulted in hyperfine transition T_2 an order of magnitude larger than the T_2 of optical transitions, ranging fro 5 to 10 ms. The increase in T_2 was not sufficient and consequently other approaches were required. ¶ Development of the critical point technique during this work was crucial to achieving further gains in T_2. The critical point technique is the application of a static magnetic field such that the Zeeman shift of the hyperfine transition of interest has no first order component, thereby nulling decohering magnetic interactions to first order. This technique also represents a global minimum for back action of the Y spin bath due to a change in the Pr spin state, allowing the assumption that the Pr ion is surrounded by a thermal bath. The critical point technique resulted in a dramatic increase of the hyperfine transition T_2 from ~10 ms to 860 ms. ¶ Satisfied that the optimal static magnetic field configuration for increasing T_2 had been achieved, dynamic magnetic field techniques, driving either the system of interest or spin bath were investigated. These techniques are broadly classed as Dynamic Decoherence Control (DDC) in the QIP community. The first DDC technique investigated was driving the Pr ion using a CPMG or Bang Bang decoupling pulse sequence. This significantly extended T_2 from 0.86 s to 70 s. This decoupling strategy has been extensively discussed for correcting phase errors in quantum computers [8, 9, 10, 11, 12, 13, 14, 15], with this work being the first application to solid state systems. ¶ Magic Angle Line Narrowing was used to investigate driving the spin bath to increase T_2. This experiment resulted in T_2 increasing from 0.84 s to 1.12 s. Both dynamic techniques introduce a periodic condition on when QIP operation can be performed without the qubits participating in the operation accumulating phase errors relative to the qubits not involved in the operation. ¶ Without using the critical point technique Dynamic Decoherence Control techniques such as the Bang Bang decoupling sequence and MALN are not useful due to the sensitivity of the Pr ion to magnetic field fluctuations. Critical point and DDC techniques are mutually beneficial since the critical point is most effective at removing high frequency perturbations while DDC techniques remove the low frequency perturbations. A further benefit of using the critical point technique is it allows changing the coupling to the spin bath without changing the spin bath dynamics. This was useful for discerning whether the limits are inherent to the DDC technique or are due to experimental limitations. ¶ Solid state systems exhibiting long T_2 are typically very specialised systems, such as 29Si dopants in an isotopically pure 28Si and therefore spin free host lattice [16]. These systems rely on on the purity of their environment to achieve long T_2. Despite possessing a long T_2, the spin system remain inherently sensitive to magnetic field fluctuations. In contrast, this work has demonstrated that decoherence times, sufficiently long to rival any solid state system [16], are achievable when the spin of interest is surrounded by a concentrated spin bath. Using the critical point technique results in a hyperfine state that is inherently insensitive to small magnetic field perturbations and therefore more robust for QIP applications.

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Fraval, Elliot. "Minimising the decoherence of rare earth ion solid state spin qubits /." View thesis entry in Australian Digital Theses Program, 2005. http://thesis.anu.edu.au/public/adt-ANU20061010.124211/index.html.

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Burcher-Jones, Cody Owen. "Mineralogical and ion-exchange leaching study of a Rare Earth Element (REE) bearing ion-adsorption clay deposit." Master's thesis, Faculty of Engineering and the Built Environment, 2018. http://hdl.handle.net/11427/30161.

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Rare earth elements (REEs), La to Lu including Y, are vital elements in manufacture of catalysts and metallurgical industries, and play a critical role in meeting future energy demands, such as through their use in permanent magnets in wind turbines. China has dominated more than 90 % of the REE market, with heavy REE (HREE) clay deposits in South China accounting for 35 % of their total REE output. This has prompted the evaluation of ion-adsorption clay (IAC) deposits in tropical regions outside China, namely Madagascar. Clay minerals such as kaolinite are part of the phyllosilicate class, containing structures of shared octahedral aluminium and tetrahedral silicon sheets. Isomorphous substitutions within the lattice leads to a charge imbalance, which accounts for negative charge on kaolinite, thus giving the ability to attract REE cations from aqueous solution to the surface of the clay particle. IAC deposits are formed from the tropical weathering of granite with REE enrichment from accessory minerals. IAC clay samples of two regolith profiles, the pedolith (A1) and saprock (A2, B and F) from northern Madagascar were collected and subjected to a suite of characterisation techniques to investigate the properties of the clay mineral. This included particle size distribution (PSD), X-ray fluorescence (XRF), X-ray diffraction (XRD), quantitative evaluation of minerals by scanning electron microscopy (QEMSCAN), inductively coupled plasma mass spectrometry (ICP-MS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The geochemical leaching characteristics of the clay mineral were investigated using a sequential leaching program, targeting ion-exchangeable REE on kaolinite, halloysite, REEorganic matter and mineral phase. Ammonium sulphate leach experiments were conducted, varying the ionic strength to determine optimum leaching concentrations. Seawater is easily available at the coastal mine, therefore simulated seawater (NaCl) experiments were conducted with the addition of ammonium sulphate to improve the REE recovery. Compound leaching agents were investigated including varying magnesium / ammonium ratios in a sulphate system as well as ammonium in a varying nitrate / sulphate ratio system. The magnesium ion was investigated to correct the Mg deficiency in soils after leaching and the nitrate ion was investigated due to its high ionic permeability in kaolinite. Ion-adsorption clay leaching includes the leaching of impurities such as Al, Fe, Mg, K, Na, Ca and Mn. Ammoniumsulphate experiments with increasing amounts of ammonium acetate were conducted. Ammonium acetate acts a buffering agent to inhibit the leaching of the main impurity Al. The texture of sample A1 (5 to 6.5 m) was homogenous, with the QEMSCAN results showing Fe minerals distributed through the kaolinite, giving it a red appearance. The saprock samples A2, B and F have a heterogeneous texture due to the preservation of the primary texture. The QEMSCAN results show that this texture is composed of pure white kaolin, kaolin with red staining due to Fe minerals, tawny staining due to Al minerals and black phases containing Mn minerals. These Mn minerals show Ce deposited as the mineral cerianite, unavailable for ion-exchange. The pedolith sample was light REE (LREE) enriched but depleted in total REE (TREE = 1 503 ppm) compared with the saprock samples (TREE = 7 006 ppm on average). The saprock samples show LREE and HREE enrichment with samples A2 and F having La / Gd ratio of 17.4 and Gd / Lu ratios of 1.2. The more crystalline samples A2 and F (Hinckley index 0.40 and 0.44 respectively) are more REE enriched than the more weathered sample B (Hinckley index 0.32). The geochemical characterisation of sample A1 showed decreasing REE recovery from LREE to HREE from kaolinite whereas sample A2 showed consistent recovery across the REEs from kaolinite with both showing little Ce recovery. The best TREE recovery for samples A1 and A2 in the chloride system achieved with was NH4 + (44.3 % and 83.1 % respectively) followed by Na+ (39.5 % and 72.2 %) and Mg2+ (28.9 % and 72.1 % respectively). For sample A1 the recovery from the kaolinite fraction was 37.7 %, halloysite 5.1 %, organic 1.6 % and mineral 55.7 %. The proportion of ion-exchangeable REE is increased in sample A2 showing a recovery from the kaolinite fraction of 66.9 %, halloysite 12.7 %, organic 3.5 % and mineral 16.9 %. The results from increasing the ionic strength of ammonium sulphate shows that TREE leachant concentration increases as the concentration increases but decreases above 0.25 M. This indicates that the ammonium sulphate concentration saturates at 0.25 M and any further lixiviant increase eliminates access to the kaolinite surface. The simulated seawater experiments indicate that some addition of ammonium sulphate is beneficial as the addition of 0.05 M ammonium sulphate almost doubled the TREE leachant concentration. However excess addition of ammonium sulphate above 0.05 M had adverse effects on the leachant concentration of the LREEs. It was concluded from the compound leaching experiments that the Mg2+ ion can be used to supplement ammonium leaching with the greatest leachant concentration using a Mg2+:NH4 + ratio of 1:2 (equal charge). This ratio would produce a high REE leachant concentration while keeping Mg available for plants (flora). Compound leaching with the nitrate ion shows that the greatest REE leachant concentration was with a NO3 - :SO4 2- ratio of 2:1 (equal charge) due to increased nitrate ion permeability. The results from the addition of ammonium acetate as a buffer showed that the buffer inhibited the leaching of Al in both samples A1 and F, with the greatest inhibition at 0.05 M. The characterisation experiments illustrate the complexity of the in-situ clay deposit and further work should use this information to construct leaching models that take into account the heterogeneity of saprock samples. The leaching experiments show that compound leaching can improve REE recovery and further work should incorporate multiple lixiviants in in-situ leaching models.

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Wood, Timothy James. "Structural studies of rare earth silicides on silicon by medium-energy ion scattering." Thesis, University of York, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.434176.

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Sakr, Hesham. "Towards mid-infrared fibre lasers : rare earth ion doped chalcogenide glasses and fibres." Thesis, University of Nottingham, 2016. http://eprints.nottingham.ac.uk/33338/.

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This Project is aimed at developing rare earth ion doped chalcogenide glasses targeting mid-infrared (MIR) fibre lasers, emitting in the wavelength region 4 - 5 μm. The work reported in this thesis has two objectives: (i) a study of the Ge-As-In-Se glass system when doped with a single species of rare earth (RE) ions, i.e. praseodymium (Pr3+) or cerium (Ce3+), or when co-doped with two rare earth ion species: Pr3+ and Ce3+, and (ii) a study of the effect of replacing a gallium (Ga) additive with an indium (In) additive on the physical and optical properties of the undoped and Pr3+ doped Ge-As-(Ga/In)-Se glasses and fibres. The MIR, i.e. 3 - 25 μm wavelength, offers to advance many photonics areas including bio-medical imaging spectroscopy for human tissue sensing in vivo for early cancer diagnosis. Low loss RE-ion doped MIR fibre lasers are potential pumps for MIR supercontinuum generation (SCG) sources for a compact MIR broadband device. Also, MIR fibre narrowband lasers offer potential new wavelengths for laser medical surgery. To date, there are no MIR rare earth ion doped glass fibre lasers emitting at wavelengths ≥ 4 μm. Selenide (Se)-based glasses, a member of the chalcogenide glass family, are known for their wide transparency up to 12 μm and good rare earth ion solubility. In the Project, an additive to the Ge-As-Se glass system of indium or gallium is considered to help decluster the rare earth ions and increase their solubility in the as-prepared Pr3+ doped Ge-As-(Ga/In)-Se glasses. However, an indium additive is concluded here to achieve a lower rare earth ion solubility limit than that obtained using the equivalent gallium additive in the Ge-As-(Ga/In)-Se glass systems. On the other hand, the photoluminescent intensity is concluded here to be approximately doubled when using an indium additive in Pr3+ doped Ge-As-In- Se, compared to the analogous gallium glasses. Furthermore, the decay lifetime, at the same emission wavelength of 4.7 μm, is found to be longer in the Pr3+ doped Ge-As-In-Se glasses when compared to the Pr3+ doped Ge-As- Ga-Se glasses. Overall, for a singly-doped Ge-As-In-Se glass system, Pr3+ offer wide photoluminescence spectral emission in the range 3 - 6 μm, which promotes this type of glass fibre as an active source for MIR laser emission in the target range of 4 - 5 μm. However, the photoluminescent decay lifetime, at 4.7 μm, of Pr3+ doped Ge-As-In-Se is concluded to decrease substantially with the number of thermal processes invoked to fabricate the glass-based fibres; a lifetime of 7 - 9 ms measured on the as-prepared fibres is compared to the decay lifetime of 9 - 10.1 ms that were found in the bulk glasses. Alternatively, the addition of Ce3+ in the Ge-As-In-Se glass system is concluded to offer a larger absorption cross-section than that of the Pr3+ in the wavelength range 3.5 - 5 μm. Co-doping the Pr3+ / Ce3+ in Ge-As-In-Se in order to enhance the MIR photoluminescence emission in the range 3 - 6 μm is also investigated. It is concluded that rare earth ions, in particular Ce3+ and / or Pr3+, doped chalcogenide glass fibres based on the Ge-As-In-Se glass system, developed through this Project, are strong candidates towards achieving MIR fibre lasers.

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Ridley, Mark K. "Gradient ion chromatographic determination of rare earth elements in coal and fly ash." Master's thesis, University of Cape Town, 1992. http://hdl.handle.net/11427/18597.

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Rare Earth Element (REE) determination in samples of coal and fly ash was undertaken by gradient high performance ion chromatography (HPIC). Ion chromatographic analysis requires that samples be in solution and that the matrix transition metals be removed. Coal samples, weighing 0.20g, were successfully dissolved in sealed pressure vessels in a microwave oven. Standard ashing procedures, followed by acid dissolution, were carried out to allow comparison with the microwave digestion technique. A lithium metaborate/tetraborate fusion and acid dissolution technique was used for the dissolution of fly ash. For the technique of REE determination the sample matrix was removed by off-line cation exchange. In an initial stage of the HPIC analysis the transition metals were removed by anion exchange using pyridine-2,6 dicarboxylic acid. The REE were then analysed using gradient elution of oxalic and diglycolic acid. Typically a 100μ1 volume of sample solution was employed for REE determination, but in the case of low ash (low REE) coal samples, prepared by microwave digestion, on-line concentration of 3-5 ml of sample, was necessary. The separated REE were reacted with 4-(2-pyridylazo)-resorcinol (PAR) and detected photometrically using a visible light detector at a wavelength of 520nm. Reproducibility for each REE was typically better than 5%CoV. Results from the analysis of coal and fly ash international standard reference materials were in acceptable agreement with values from alternative analytical procedures. Smooth, coherent trends obtained when the data were plotted on chondrite and "shale composite" normalised diagrams provided some support for the accuracy of the technique. The application of HPIC to the determination of REE in coals was demonstrated by the analysis of a new international reference coal sample, USGS CLB-1. Differences in REE concentrations between coal samples prepared by microwave digestion and ashing were observed. The HPIC analytical technique was also applied to the determination of REE in fly ash. The REE concentrations of fly ash from sequential electrostatic precipitators, from Lethabo and Kendal power stations, were determined to elucidate the behaviour of REE after the combustion of coal. REE concentrations increased through the sequential precipitators.

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Gonçalves, Tássia de Souza. "Caracterização estrutural e espectroscópica de vidros fluorofosfatos dopados e co-dopados com Er3+ e Yb3+." Universidade de São Paulo, 2014. http://www.teses.usp.br/teses/disponiveis/18/18158/tde-18082014-150349/.

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Atualmente, vidros e vitrocerâmicas dopados com íons terras raras trivalentes TR3+ constituem a mais importante classe de materiais para aplicações laser e em outros dispositivos ópticos, na região do infravermelho próximo e visível. Neste contexto, um dos desafios está em encontrar uma matriz hospedeira adequada que assegure qualidade óptica e um ótimo desempenho dos íons dopantes (altas seções de choque de absorção e emissão, baixa probabilidade de decaimentos não radiativos, tempos de vida de estado excitado suficientemente longos), mantendo estabilidade térmica e mecânica. Entre os possíveis candidatos, estão os vidros fosfatos com alta capacidade de dispersão dos dopantes, baixo índice de refração e propriedades termo-ópticas superiores aos silicatos, calcogenetos e fluoretos. Contudo, estes vidros apresentam alta energia de fônons, menor estabilidade química e mecânica e são higroscópicos, o que pode constituir um significativo mecanismo de supressão da luminescência devido ao acoplamento de transições dos TR3+ com vibrações de grupos hidroxila. Se por um lado vidros fluoretos podem ser obtidos com baixas energias de fônon e alta estabilidade química, os mesmos são mecanicamente frágeis e apresentam más características termo-ópticas. Para superar estas limitações, vidros oxifluoretos como fluorofosfatos têm sido explorados com a promessa de combinar os méritos dos fluoretos (baixas energias de fônon, baixos índices de refração, extensa janela de transmissão óptica) e dos óxidos (alta estabilidade química e resistência mecânica, maior solubilidade dos TR3+). Do ponto de vista das aplicações, considerando a transmissão e amplificação de sinais em telecomunicação em torno de 1,5 µm, e geração de ação laser de alta potência em torno de 1,0 µm, materiais dopados com Er3+ e Yb3+ estão entre os mais importantes. Neste trabalho apresenta-se a síntese e caracterização estrutural e espectroscópica de novos vidros fluorofosfatos dopados com Er3+ ou Yb3+ e co-dopados com ambos, no sistema composicional 25BaF225SrF2(30-x)Al(PO3)3xAlF3 (20-z)YF3:zTRF3 com x = 20 ou 15, TR = Er3+ e/ou Yb3+ e z = 0,25, 0,5, 1,0, 2,0, 3,0, 4,0 e 5,0 mol%. As amostras foram obtidas pelo método convencional de fusão e resfriamento e caracterizadas por Raman, Ressonância Magnética Nuclear de estado sólido e espectroscopia UV-VIS. Dos estudos por RMN de 19F verificou-se que há uma perda máxima de fluoreto de ~20% nas amostras. Ainda assim, a quantidade remanescente foi suficiente para garantir um ambiente químico favorável às emissões e poucas diferenças foram notadas entre as amostras com 20 e 15 mol% AlF3 contendo a mesma concentração de dopantes. Para o Er3+, tempos de vida do estado emissor 4I13/2 da ordem de 10 ms implicam em altos valores de eficiência quântica (η= 85%) e para o Yb3+ tempos de vida do estado emissor 2F5/2 similarmente longos (τ = 1,7 ms) foram medidos. Em amostras co-dopadas com 4,0 mol% YbF3 e 0,25, 1,0 e 2,0 mol% ErF3 o decréscimo do tempo de vida do Yb3+ e acréscimo do tempo de vida do Er3+ indicam que a transferência Yb→Er foi eficiente neste sistema. De maneira geral, os resultados indicam que os vidros estudados são potenciais candidatos a aplicações ópticas como as mencionadas acima.
Currently, glasses and glass ceramics doped with trivalent rare earth ions RE3+ represent the most important class of materials for laser and other optical applications in the visible and near-infrared spectral regions. In this context, one of the challenges is to find host matrices that assure good optical quality and optimum performance of the dopant ions (high absorption and emission cross sections, low probability of non-radiative decays, sufficiently long excited state lifetimes), while still maintaining thermal and mechanical stabilities. Among the candidates, phosphate glasses with high capacity for RE3+ dispersion, low refractive index and superior thermo-optical properties than silicate, chalcogenide and fluoride glasses are largely studied. However, phosphates present high phonon energies, lower chemical and mechanical stabilities and they are hygroscopic, which can imply in significant luminescence quenching effects. If on one hand fluoride glasses may be designed with low phonon energies and higher chemical stability, they are frail and present less than ideal thermo-optical properties. In order to overcome these drawbacks, oxyfluoride glasses such as fluorophosphates have been explored with the promise to combine the merits of fluorides (low phonon energies and refractive index, extensive optical window) and of oxides (high chemical stability and chemical resistance, higher solubility of RE3+). From the viewpoint of applications, when it comes to the transmission and amplification of signal in telecommunications around 1.5 µm, and the generation of high power lasers around 1.0 µm, materials doped with Er3+ and Yb3+ are among the favorite. Furthermore, because Yb3+ presents higher absorption cross-section than Er3+ at the preferred excitation wavelength for both these ions (980 nm), the former can act as an efficient sensitizer of excitation energy with subsequent transfer to the latter. We present the synthesis, and structural and spectroscopic characterization of new flurophosphate glasses doped with Er3+ or Yb3+ and co-doped with both, in the compositional system 25BaF225SrF2(30x)Al(PO3)3 xAlF3 (20- z)YF3:zREF3 with x = 20 or 15, RE = Er3+ and/or Yb3+ and z = 0.25, 0.5, 1.0, 2.0, 3.0, 4.0 and 5.0 mol%. The samples were obtained by conventional melt quenching technique and characterized by Raman, solid state NMR and UV-VIS spectroscopy. From the NMR studies of 19F, it was shown that there is a maximum fluoride loss of 20% in the samples. Even so, the remaining quantity was enough to assure a favorable chemical environment to the RE3+ emissions. Little differences were detected between the samples with 20 and 15 mol% AlF3 for the same dopant concentration. For Er3+, lifetimes of the emitting level 4I13/2 of the order of 10 ms result in fluorescence quantum efficiency values (η = 85%), and similarly, for Yb3+, long lifetimes of the excited state 2F5/2 (τ = 1,7 ms) were measured. In co-doped samples with 4.0 mol% YbF3 and 0.25, 1.0 and 2.0 mol% ErF3 the decrease in lifetime of Yb3+ and increase in lifetime of Er3+ indicate that the Yb→Er energy transfer is efficient in this system. In general, the results indicate that the studied glasses are potential candidates for optical applications.

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Aðalsteinsson, Sigurbjörn Már. "Study of rare-earth oxy-hydrides as candidates for photochromic materials." Thesis, Uppsala universitet, Tillämpad kärnfysik, 2019. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-396533.

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Sampaio, Jurací Aparecido. "Preparação e caracterização de vidros aluminato de cálcio com baixa concentração de sílica dopados com Nd2O3 e Er2O3." Universidade de São Paulo, 2001. http://www.teses.usp.br/teses/disponiveis/76/76132/tde-24062008-162022/.

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O desenvolvimento de laseres de estado sólido compacto operando na região do infravermelho médio, entre 2 - 5 ?m, tem recebido considerável atenção nos últimos anos. Esses dispositivos oferecem grande potencial como fonte de luz para uma infinidade de aplicações, como por exemplo laseres para medicina e sensores químicos remotos. Laseres operando na região de 2.8 ?m tem interesse particular na medicina devido a forte banda de absorção da água nessa região espectral. Para se conseguir forte emissão laser próximo a 2.8 ?m têm sido investigadas famílias de vidros não-óxidos, como por exemplo vidros fluoretos de metais pesados e vidros chalcogenetos, dopados com Er3+. Entretanto esses vidros são caros, difíceis de serem feitos, além de serem tóxicos. Por essa razão o desenvolvimento de um vidro óxido seria ideal, já que são mais baratos, relativamente fáceis de serem produzidos, além de não serem tóxicos. A desvantagem dos vidros óxidos é a sua alta energia de fônons, quando comparada aos vidros haletos e chalcogenetos, que aumenta a taxa de transição não radiativa. Seria interessante investigar um sistema vítreo que tivesse propriedades otimizadas, ou seja, boas propriedades ópticas, térmicas e mecânicas, e baixa energia de fônons. O sistema vítreo aluminato de cálcio seria um candidato para essas aplicações, já que preenche essas exigências. Porém não há na literatura informações a respeito da influência de pequenas quantidades de elementos terras raras nas propriedades desses vidros, e qual é a concentração ideal desses íons. O objetivo dessa tese foi investigar composições de vidros aluminato de cálcio (48,1 CaO : 40.8 Al2O3 : 4.1 MgO : 7.0 SiO2) dopados com Nd2O3, Er2O3 ou Yb2O3, e verificar qual a influência desses íons nas propriedades ópticas, térmicas, mecânicas e termo-ópticas. Investigou-se também qual a influência da atmosfera de fusão. Com esse objetivo as amostras foram fundidas em cadinhos de grafite sob vácuo, e em cadinhos de platina, ao ar, ambas as fusões ocorreram a 1400 °C. As amostras foram investigadas através de difração de raios-X e microscopia óptica, cujos resultados confirmaram o estado amorfo das amostras preparadas. As amostras não apresentaram estrias e tiveram boa transparência óptica. Os espectros de transmitância mostraram que o processo de fusão a vácuo eliminou completamente a forte banda de absorção próxima a 3 ?m devida a água. O corte da transmitância na região do infravermelho ocorreu em 5.5 ?m, sendo independente do tipo do íon terra rara presente na composição do vidro. O índice de refração em 546.1 nm aumentou de 1.6702 (amostra base) para 1.6876 (amostra dopada com 8% de Er2O3). Este acréscimo no índice de refração é atribuído a um aumento da polarizabilidade eletrônica do vidro devido ao aumento de oxigênios nonbridging. A densidade aumenta de 2.92 g/cm3 (amostra base) para 3.12 g/cm3 (amostra dopada com 8% de Er2O3), esse aumento é explicado levando em consideração a massa dos átomos terras raras, que são maiores em relação ao Al2O3. A dureza dos vidros aluminato de cálcio diminuiu de 865 kg/mm2 (amostra base) para 781 kg/mm2 (amostra dopada com 8% de Er2O3), ou seja aproximadamente 11% de decréscimo. No caso da temperatura de transição vítrea, Tg, esse decréscimo é de aproximadamente 8%, sendo 841 °C para a amostra base e 782 °C para a amostra dopada com 8% de Er2O3. Para o vidro base, a difusividade térmica foi de 5.75 x 10-3 cm2/s e a condutividade térmica foi de 15.5 x 10-3 cm-1 K-1. Tanto a difusividade quanto a condutividade térmica decresceram na mesma proporção da dureza e Tg, conforme substitui-se a alumina pelo óxido terra rara. Esta é uma indicação de que os átomos terras raras atuam como modificadores de rede, abrindo a estrutura do vidro, diminuindo a resistência mecânica e atuando como barreiras térmicas no material. A resistência ao choque térmico dos vidros aluminato de cálcio é de 339 W/m, semelhante aos vidros silicatos que é de 358 W/m, e aproximadamente quatro vezes maior que a dos vidros fluoretos, 86 W/m. Este resultado confirma a hipótese de que os vidros aluminato de cálcio podem suportar variações abruptas de temperatura. Através da espectroscopia de lente térmica foram obtidas a eficiência quântica dos vidros aluminato de cálcio dopados com Nd2O3 e Er2O3. No caso das amostras dopadas com concentrações menores de 3% de Nd2O3 a eficiência quântica foi de aproximadamente 80%. Esses resultados indicam que os vidros aluminato de cálcio são excelentes candidatos para laseres de estado sólido e demais aplicações ópticas na região do infravermelho médio.
The development of compact solid-state lasers operating in the midinfrared wavelength region (2 -5 ?m) has been an area of considerable activity in the last few years. These devices offer great potential as light sources for applications as medical lasers as well as in remote chemical sensing devices. Light sources in the 2.8?m region are of particular interest for medical applications due to the strong water absorption in this spectral region. Apart from allowing extremely precise cutting and ablation of water-containing tissues, the other advantages of using light sources operating at 2.8 ?m are related to the possibilities of reducing skin burning in surgeries, decrease in the use of anesthesia and shortening of recovery time, especially in skin surgeries and in the cutting and remova1 of hard tissues, such as tooth enamel and bone. In order to achieve strong laser emission around 2.8 ?m the effort so far has been concentrated on the family of Er3+ doped non -oxide glasses such as heavy metal fluorides and chalcogenides. However the production of these glasses is expensive, and it is difficult to make them, besides they are toxic. On the other hand, the oxide glasses are cheaper, atoxic and easy to produce them. The disadvantaged, however, is its the relative high phonon energy that promote high nonradiative transition rates. Since calcium aluminate glasses are formed with non-network forms, CaO and Al2O3, they have high tendence towards devitrification. The addition of small amounts of alkali and alkaline earth elements enlarges the glass forming region. Several calcium aluminate glasses compostions containing SiO2, BaO and MgO are now reported in the literature. In this thesis, low silica calcium aluminosilicate glasses doped with Nd2O3 and Er2O3 were prepared. Since the sample compositions were close to the phase diagram glass formation, the rare earth doping was performed up to 8wt.%. The samples was melted under vacuum condition in a graphite crucible at 1500 °C, and in air in a platinum crucible. The influence of the rare earth doping on the thermal diffusivity, thermal conductivity and Vickers hardness was such that all these physical parameters decreased by roughly the same amount, namely 8%, between the undoped and 5 wt% of Nd2O3. The dependence of these parameters, as a function of the Nd2O3 doping, strongly supports the idea that the Nd3+ or Er3+ act as network modifiers. Elastic module (E, G, K, v) of calcium aluminosilicate glasses with < 10 mole% of SiO2 doped with Er2O3 and Yb2O3, melted in air and under vacuum conditions, have been measured using the pulse echo ultrasonic technique. There was a decrease of the elastic properties, about 5%, as rare earth doping increases from 0.2 to 1.5-mol% (about 8 wt%). The Young\'s modulus did not vary within errors of measurements. The Debye temperature varied between (369±9)K and 352±9 K, which is explained assuming that the rare earth ions acts as network modifiers disrupting the glasses structure. The undoped calcium aluminate glasses fracture toughness is (1.4±0.3) MPa m1/2 and the thermal shock resistance is (339±102) W/m. The fluorescence quantum efficiency determined by thermal lens spectroscopy, was found be about 80% for the 2wt% Nd2O3 doped calcium aluminosilicate glass. The fluorescence quenching was observed to doping higher than 2wt% Nd2O3. The variation of the refractive index as a function of the temperature, dn/dT, was found be 8.0 x 10-6/0c. Among the various glass system investigated, CA glasses presented greater mechanical properties and larger thermal shock resistance, indicating that these materials are candidates for solid state laser applications and other infrared applications.

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Rastrelo, Lara Rossana. "Síntese, caracterização e fotoluminescência de titanatos de cálcio dopados com íons Tm³+, Tb³+ e Sm³+." Universidade Federal de Goiás, 2013. http://repositorio.bc.ufg.br/tede/handle/tede/4675.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES
The photoluminescent properties (FL) has always aroused the interest of the scientific community, especially after the discovery of photoluminescence at room temperature, which favors applications in new optical-electronic devices. This work used the Polymeric Precursors Method to obtain CTO doped with rare earth ion: Tm3+, Tb3+ and Sm3+. The materials: CTO:Sm1,2%,Tb0,3%,Tm0,5% and CTO:Sm2%,Tb0,3%,Tm0,5% were calcined at temperatures of 450, 500, 550 and 600 ° C in order to correlate structural changes and photoluminescence emission. Other materials: CTO:Sm1,2%,Tm0,5%, CTO:Tm0,5%,Tb0,3%, CTO:Sm1,2%,Tb0,3%, CTO:Sm1,2%Tb0,3%, CTO:Tb0,3%, CTO:Tm0,5%, CTO:Sm1,2% and CTO:Sm2% were calcined at 600 ° C in order to comprehend the influence of rare earth ions in photoluminescence emission process. The structural organization of the materials over long distances CTO:Sm1,2%,Tb0,3%,Tm0,5% was correlated with the emission FL. The FL intensity can be linked directly to the structural system, and the material totally disorganized or completely organized does not present FL emission. The material CTO:Sm1,2%,Tb0,3%,Tm0,5% showed the highest intensity FL to materials heat treated at 500oC, while the material CTO:Sm2%,Tb0,3%,Tm0,5% showed the highest intensity FL to materials heat treated at 450 oC. The electronic transitions from rare earth ions was observed to the obtained materials.
A propriedade fotoluminescente (FL) sempre despertou o interesse da comunidade científica, principalmente a partir da descoberta da fotoluminescência a temperatura ambiente, o que favorece uma infinidade de aplicações em novos dispositivos óptico-eletrônicos. Neste trabalho sintetizaram-se pelo Método dos Precursores Poliméricos matrizes de CTO dopado com os íons Tm3+, Tb3+ e Sm3+. Os materiais: CTO:Sm1,2%,Tb0,3%,Tm0,5% e CTO:Sm1,2%,Tb0,3%,Tm0,5% foram calcinados nas temperaturas de 450, 500, 550 e 600ºC para a comparação de evolução estrutural e fotoluminescência. Outros materiais: CTO:Sm1,2%,Tm0,5%, CTO:Tm0,5%,Tb0,3%, CTO:Sm1,2%,Tb0,3%, CTO:Sm1,2%Tb0,3%, CTO:Tb0,3%, CTO:Tm0,5%, CTO:Sm1,2% e CTO:Sm2% foram calcinados a 600ºC para estudar a emissão apenas dos íons adicionados na matriz. A organização estrutural dos materiais a longa distância do CTO:Sm1,2%,Tb0,3%,Tm0,5% foi comparada com a emissão FL. A intensidade FL esta ligada diretamente ao ordenamento estrutural, se o material estiver totalmente desorganizado ou totalmente organizado não haverá emissão FL. O material CTO:Sm1,2%,Tb0,3%,Tm0,5% calcinado a 500ºC apresentou a maior intensidade FL. O material CTO:Sm2%,Tb0,3%,Tm0,5% quando calcinado a 450ºC apresentou a maior intensidade FL. Após a análise dos dados referentes à caracterização dos materiais foi possível atribuir às transições eletrônicas que ocorrem com os íons terras-raras e a influência da inserção de mais de um íon dopante na matriz titanato de cálcio na emissão FL.

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Aull, Brian Francis. "The impact of ion-host interactions on the 5d-to-4f spectra of lanthanide rare earth ions." Thesis, Massachusetts Institute of Technology, 1985. http://hdl.handle.net/1721.1/40343.

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Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Electrical Engineering and Computer Science, 1985.
MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING.
Includes bibliographical references.
by Brian Francis Aull.
Ph.D.

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Pinto, Ricardo de Almeida. "Síntese e caracterização de vidros de telureto dopados com íons de Eu3+ e Tb3+ com nanopartículas metálicas." Universidade de São Paulo, 2009. http://www.teses.usp.br/teses/disponiveis/3/3140/tde-29062009-124648/.

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Neste trabalho são apresentadas a síntese e caracterização das propriedades luminescentes dos sistemas vítreos TeO2-ZnO e TeO2-ZnO-PbO-Na2O dopados com íons de európio e térbio contendo nanopartículas (NPs) metálicas de prata, ouro e cobre, para aplicações em dispositivos fotônicos. Estes vidros possuem uma larga região de transmissão (350-6500 nm), elevada estabilidade química, resistências mecânica e térmica, baixa energia de fônon (em torno de 700 cm-1) e alto índice de refração (~ 2,0). Por meio de medidas de absorção óptica foi observada a incorporação dos íons de terras-raras na forma trivalente, responsável pelo fenômeno de luminescência nos vidros e a presença de bandas de absorção relacionadas à ressonância dos plasmons superficiais (RPS), localizadas em aproximadamente 490 nm (no caso das NPs de prata), em 500 nm (no caso das NPs de ouro) e em torno de 800 nm (no caso das NPs de cobre). A caracterização das NPs metálicas foi realizada por meio da Microscopia Eletrônica de transmissão auxiliada pelas técnicas de difração de elétrons e espectrometria de energia dispersiva (EDS) e permitiu a observação de NPs metálicas, cristalinas e de diversos formatos e tamanhos. As medidas de emissão foram realizadas excitando as amostras em 405 nm para as dopadas com Eu3+ e 377 nm para as amostras dopadas com Tb3+, por meio de um espectrômetro de fluorescência, com lâmpada de Xenon de pulsos de 2 a 3 s. Foram medidas bandas de emissão associadas à emissão do Eu3+ em 580 nm, 590 nm, 614 nm, 650 nm e 695 nm devidas às transições 5D07FJ (com J = 0 até 4). A banda situada em 614 nm, associada a uma transição de dipolo-elétrico é a mais intensa, por ser mais sensível às mudanças do campo local provocado pela presença das NPs metálicas. Para as amostras dopadas com Tb3+ foram observadas emissões em 485 nm, 550 nm, 590 nm e 623 nm, associadas às transições 5D47FJ (com J = 6 até 3), sendo a emissão em 550 nm associada também a uma transição de dipolo-elétrico e portanto a mais sensível às alterações do campo local provocado pela presença das NPs metálicas. Para as amostras codopadas com íons de Eu3+ e Tb3+, foram observados aumentos significativos da luminescência referente à emissão em 614 nm na presença de NPs de prata. A obtenção de aumento da luminescência dos íons de Eu3+ somente pela transferência de energia proveniente do Tb3+ não é um mecanismo trivial. Entretanto, foi observado em amostras preparadas com diferentes concentrações de íons aceitadores e doadores e intensificada também na presença de NPs de prata. Os aumentos ocorridos na luminescência são provavelmente causados pelo aumento do campo local nas proximidades dos íons de terras-raras e por processos de transferência entre as NPs metálicas e os íons de terras-raras. Nestes casos a distância entre os íons de terras-raras e as NPs está compreendida entre 5 nm e 20 nm. Portanto, a presença das NP desempenha um papel importante para o aumento da luminescência, permitindo o desenvolvimento de novos materiais com aplicações em nanofotônica.
This work presents the synthesis and characterization of luminescent properties of vitreous systems TeO2-ZnO e TeO2-ZnO-PbO-Na2O doped with ions of europium and terbium containing silver, gold and copper nanoparticles (NPs), for applications in photonic devices. These glasses have a large window transmission (350-6500 nm), chemical stability, mechanical and thermal resistance, low phonon energy (around 700 cm-1) and high refraction index (~2,0). The optical absorption measurement showed the incorporation of rareearths ions in the trivalent form, responsible for the luminescence phenomenon in the glasses and the presence of absorption bands related to the surface plasmons resonance (SPR), located in approximately 490 nm (in the case of silver NPs) in 500 nm (in the case of gold NPs) and around 800 nm (in the case of copper NPs). The characterization of the metallic NPs was perfomed with transmission electron microscopy (TEM) with the aid of electron diffraction and energy dispersive spectroscopy techniques that allowed the observation of metallic NPs, crystalline with several shapes and sizes. The measurements were made through with excitation of 405 nm for samples doped with Eu3+ and 377 nm for samples doped with Tb3+, using a fluorescence spectrometer, with Xenon lamp with pulses varying from 2 to 3 s. The bands associated to Eu3+ emission were measured at 580 nm, 590 nm, 614 nm, 650 nm and 695 nm due to the transitions 5D07FJ (with J = 0 to 4). The band situated at 614 nm related to electric dipole transition is the most intense because it is sensitive to changes in the local field, caused by the presence of metallic NPs. For samples doped with Tb3+ it was observed emissions at 485 nm, 550 nm, 590 nm and 623 nm, associated with the transitions 5D47FJ (with J = 6 to 3) being the 550 nm emission also related to electric dipole transition and consequently the most sensitive to changes in the local field, caused by the presence of metallic NPs. For the samples codoped with Eu3+ and Tb3+ ions it was observed significative enhancement of the luminescence at 614 nm emission in the presence of silver NPs. The achievement of the enhancement of the luminescence of Eu3+ ions only by energy transfer from Tb3+ is not a trivial mechanism. However, it was observed in samples prepared with different concentrations of acceptor and donors ions and intensified in the presence of NPs silver. The enhancement of the luminescence is probably caused by the increase of the local field around the rare earth ions and by processes of energy transfer between the metallic NPs and the rare earth ions. In these cases the distance between the rare earth ions and the metallic NPs ranges from 5 to 20 nm. Thus, the presence of metallic NPs plays an important role for the enhancement of the luminescence, allowing the development of new materials with application in photonic.

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Mishra, Jayanta Kumar [Verfasser], and A. [Akademischer Betreuer] Hangleiter. "Optical study of rare earth ion and transition metal impurities in nitrides / Jayanta Kumar Mishra ; Betreuer: A. Hangleiter." Braunschweig : Technische Universität Braunschweig, 2013. http://d-nb.info/1175822221/34.

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Mello, Laura Bissoli de 1987. "Propriedades estruturais e óticas de vidros germanoniobofosfato dopados com íons terras raras." [s.n.], 2013. http://repositorio.unicamp.br/jspui/handle/REPOSIP/250548.

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

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Santos, Allysonn Jorge dos. "Sensor óptico de temperatura baseado no processo de conversão ascendente de energia em vidros fluorofosfatos dopados com Er3+." Universidade de São Paulo, 2016. http://www.teses.usp.br/teses/disponiveis/18/18158/tde-03052016-090614/.

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O processo de conversão ascendente de energia (infravermelho ao visível) é amplamente estudado em materiais dopados com íons terras raras trivalentes (TR3+) devido as várias possibilidades de aplicações tecnológicas. Tal processo consiste na emissão de fótons de maior energia (usualmente no visível) mediante excitação com fótons de menor energia (infravermelho) via mecanismo de absorção de dois fótons e/ou transferência de energia entre os íons TR3+. Entre os materiais estudados destacam-se vidros e vitrocerâmicas dopados com Er3+ com emissões nas regiões do verde e do vermelho, que podem ser eficientemente excitadas por lasers de diodo na região do infravermelho próximo (980 nm). Uma das aplicações possíveis para este processo é a de um sensor óptico de temperatura baseado na dependência da razão de intensidades de emissão dos níveis 2H11/2 e 4S3/2 do Er3+ com a temperatura, vantajoso para operação em ambientes hostis como transformadores de alta tensão, em processos industriais, etc. Como a eficiência das emissões depende também da matriz hospedeira, os vidros fluorofosfatos com composição 25BaF225SrF2(30-x)Al(PO3)3xAlF3(20-z)YF3:zErF3 com x = 20 e z = 1,0 a 5,0 mol% foram escolhidos por apresentarem alta estabilidade química e mecânica, e energia de fônon relativamente baixa. Assim, amostras vítreas dopadas com várias concentrações de Er3+ foram previamente caracterizadas e selecionadas para desenvolver o protótipo que emprega a variação de intensidade relativa das emissões 2H11/2 → 4I15/2 e 4S3/2 → 4I15/2 do vidro fluorofosfato dopado com Er3+ na medição de temperaturas. Este protótipo apresenta as características de baixo custo, alta sensibilidade e rápida resposta.
The infrared-to-visible upconversion process is widely studied in materials doped with trivalent rare earth ions (RE3+) due to the various possibilities of technological applications. The process is based on the emission of photons with higher energy (in the visible) than the excitation photons (in the infrared) via the mechanisms of two-photon absorption and/or energy transfer between RE3+ ions. Among the studied materials emphasis is given to glasses and glass ceramics doped with Er3+, exhibiting intense emissions in the green and red, which can be efficiently excited by diode lasers in the near infrared region (980 nm). One application of this process is an optical temperature sensor based on the dependence of the ratio of the emission intensities of levels 2H11/2 and 4S3/2 of Er3+ on the temperature of the sample. Such sensor would be advantageous for operation in hostile environments, such as high voltage transformers, industrial processes, etc. Because the efficiency of upconversion also depends on the host matrix composition, flurophosphate glasses are interesting candidates due to their high chemical stability, good mechanical properties and relatively low phonon energy. Glasses with composition 25BaF225SrF2(30-x)Al(PO3)3xAlF3(20-z)YF3:zErF3 with x = 20 and z varying from 1.0 to 5.0 mol% were characterized and selected to develop the prototype employing the fluorescence of fluorophosphate glass doped with Er3+ for measuring temperatures with the following characteristics: low cost, high accuracy and fast response.

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Martins, Vanessa Menezes. "Desenvolvimento e caracterização fototérmica de novos materiais vítreos dopados com íons emissores terras-raras." Universidade Federal de Uberlândia, 2009. https://repositorio.ufu.br/handle/123456789/19674.

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CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
Neste trabalho foram desenvolvidas duas novas matrizes vítreas, uma fosfato e outra borato, denominadas PAN (40P2O5.20 Al2O3.40Na2CO3 (mol%)) e BAN (40B2O3.20 Al2O3 . 40Na2CO3 (mol%)), respectivamente. Estas matrizes foram dopadas com concentrações crescentes de íons de neodímio e praseodímio, visando o estudo de propriedades ópticas e térmicas nos mesmos. Para obter estas propriedades, inicialmente foram realizadas medidas de absorção óptica, fotoluminescência, tempo de vida, índice de refração, densidade mássica e calor específico. Em seguida aplicando a técnica de lente térmica de feixe duplo no modo descasado resolvida no tempo foram obtidas as propriedades fototérmicas das amostras. Verificou-se que as difusividades térmicas das matrizes PAN e BAN apresentaram valores similares. Determinou-se também a eficiência quântica de fluorescência das amostras dopadas com neodímio, através da técnica de lente térmica com o uso da amostra referência. Neste estudo ficou claro que a inserção de íons dopantes nas matrizes causa um efeito de supressão na luminescência. Este efeito tornou- se mais evidente na diminuição da eficiência quântica (e do tempo de vida) com o aumento da concentração. Por fim, à partir dos resultados da eficiência quântica e do tempo de vida, pôde-se calcular a taxa de decaimento não radiativo. Todos os resultados foram analisados em função da concentração de dopante, e em particular, para o caso do íon de neodímio inseridos na matriz PAN, constatou-se que estes vidros possuem uma boa combinação das propriedades termo- ópticas, que são essenciais para possíveis aplicações em materiais para meio ativo em lasers de estado sólido.
In this work two new glass matrices has been developed, a phosphate and borate one, PAN (40P2O5.20 Al2O3. 40Na2CO3 (mol%)) and BAN (40B2O3. 20 M2O3. 40Na2CO3 (mol%)), namely. The matrices were doped with increasing concentration of neodimium and praseodymium rare-earth ions in order to study its thermal and optical properties. To obtain these properties, initially, measurements of optical absorption, photoluminescence, lifetime, refractive index, mass density and specific heat were performed. In addition, applying the time resolved mode mismatched dual beam thermal lens technique the thermal-optical properties were found. It was found that the PAN and BAN thermal diffusivities were quite similar. By using a reference sample the quantum efficiency of the neodymium sample were determined. It was noticed that the insertion of dopant fens causes a luminescence quenching. This effect became more evident in the decreasing of the quantum efficiency (and lifetime) when concentration is increased. Finally, from the above results it was possible to calculate the nonradiative relaxation rate. All the found results were analised as a function of concentration. In particular, the PAN matrix presents a good combination of thermal and optical properties, which are essential to possible aplication in optical devices.
Dissertação (Mestrado)

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Assumpção, Thiago Alexandre Alves de. "Desenvolvimento de técnica para nucleação de nanopartículas metálicas em vidros de germanato dopados com íons de túlio para aplicações em dispositivos fotônicos." Universidade de São Paulo, 2010. http://www.teses.usp.br/teses/disponiveis/3/3140/tde-18082010-163909/.

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Neste trabalho são apresentadas a preparação, a metodologia adotada para a nucleação de nanopartículas (NPs) de prata e a investigação das propriedades luminescentes do sistema vítreo GeO2-PbO dopado com íons de túlio e codopado com íons de túlio e itérbio, na presença de NPs de prata, visando aplicação em dispositivos fotônicos. Este sistema vítreo apresenta uma larga janela de transmissão (400 4500 nm) quando comparado aos silicatos, boratos e fosfatos, alto índice de refração (2,0), baixas energia de fônon (700 cm-1), alta resistência mecânica e durabilidade química. Com a finalidade de se obter maior controle sobre o processo de nucleação das NPs, realizaram-se tratamentos térmicos de várias formas, variando-se principalmente as grandezas tempo e temperatura. A partir da Microscopia Eletrônica de Transmissão (MET), a presença das NPs no material vítreo pôde ser confirmada, e pelas análises de Espectroscopia de Energia Dispersiva (EDS Energy Dispersive Spectroscopy), determinamos que as NPs possuem em sua composição prata, podendo elas serem puramente metálicas, e em alguns casos, compostas de prata e elementos da matriz. As medidas de absorção evidenciaram a incorporação dos íons Tm3+ e Yb3+ na forma trivalente, e a presença das bandas de absorção associadas à Ressonância dos Plasmons Superficiais (RPS) da prata, localizadas no intervalo de 420 a 550 nm. Foram medidas as bandas associadas à conversão ascendente (CA) do Tm3+ em 480, 650 e 800 nm, devidas às transições 1G4 3H6, 1G4 3F4, 3H4 3H6, respectivamente. Nas amostras contendo NPs de prata, tratadas a 420 °C, não foi observada a banda de RPS da prata. Entretanto, um aumento na luminescência foi verificado, assim como a presença das NPs por MET. No caso das amostras tratadas por intervalos de tempo contínuos e não-contínuos, observamos a tendência de formação de NPs menores, maiores e agregados, e maior tendência de aumento da luminescência para o segundo caso; no caso da variação da temperatura, observamos a formação da banda de RPS da prata para tratamentos superiores a 500 °C realizados em curto intervalo de tempo, e um aumento considerável da luminescência. As variações no processo de nucleação das NPs foram relacionadas às formas de tratamento adotadas. O estudo da variação da intensidade de luminescência em função da potência do laser de excitação mostrou que as NPs não interferem nos processos de CA dos íons Tm3+. Desta forma, o aumento da luminescência foi atribuído ao aumento do campo local nas proximidades dos íons de terras-raras (TRs). Portanto, o desenvolvimento de um método adequado de tratamento térmico desempenha um papel fundamental no processo de nucleação das NPs, e pode permitir um aumento considerável da luminescência proveniente dos íons de TRs, e conferir novas propriedades aos materiais e aplicações em dispositivos fotônicos.
This work presents the preparation and the methodology used for the nucleation of silver nanoparticles (NPs), and the investigation of the luminescent properties of PbO-GeO2 glass system doped with thulium ions and codoped with thulium and ytterbium ions, in the presence of NPs silver, for application in photonic devices. This glass system presents a large transmission window (400 4500 nm) when compared to silicates, borates and phosphates, high refractive index (2.0), low phonon energy (700 cm-1), high mechanical strength and chemical durability. In order to obtain greater control over the process of nucleation of NPs, different processes were used for the heat-treatment, varying mainly the time and the temperature. From the transmission electron microscopy (TEM), the presence of NPs in the glassy material could be confirmed, and from Energy Dispersive Spectroscopy (EDS) analysis, it was determined that the NPs have silver in their composition. The NPs may be purely metallic and, in some cases, composed by silver and elements of the matrix glass. Optical Absorption measurements showed the incorporation of Tm3+ and Yb3+ ions in the trivalent form, and the presence of absorption bands related to the Surface Plasmon Resonance (SPR) of silver, located in the range of 420 to 550 nm. Bands associated to Tm3+ upconversion (UPC) frequency centered around 480, 650 and 800 nm were observed due to transitions 1G4 3H6, 1G4 3F4, 3H4 3H6, respectively. The SPR of silver NPs were not observed for the samples heat-treated at 420 °C, which contained silver NPs in their composition. However, an increase in the luminescence was observed and the presence of NPs was confirmed by TEM analyses. For the samples heat-treated by continuous and non-continuous time intervals, we observed the tendency of the formation of smaller, larger and aggregated NPs, and a higher tendency of enhancement of the luminescence for the second case. For the samples heat-treated at different temperatures in short time interval, we observed the formation of the SPR band for temperatures higher than 500 °C, and a considerable increase in the luminescence. Variations in the process of NPs nucleation were related to the different heat-treatments adopted. The study of the luminescence intensity variation as function of the laser power excitation showed that the NPs do not interfere in the Tm3+ UPC luminescence processes. Thus, the enhancement in the luminescence was attributed to local field enhancement in the proximities of rare-earth ions (REIs). Therefore, the development of an appropriate method of heat-treatment plays an important role in the process of NPs nucleation, and enables a considerable increase in the luminescence from the REIs, and gives new properties to materials which are of great interest for applications in photonic devices.

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Silva, Diego Silvério da. "Vidros de germanato com nanopartículas metálicas e semicondutoras dopados com terras-raras para aplicações em fotônica." Universidade de São Paulo, 2010. http://www.teses.usp.br/teses/disponiveis/3/3140/tde-06122010-103231/.

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Neste trabalho é apresentado um estudo espectroscópico sobre vidros de germanato contendo nanopartículas (NPs) metálicas e semicondutoras dopados com íons de terras-raras (TRs) Eu3+, Nd3+ e Er3+ visando o desenvolvimento de novos materiais para aplicações em fotônica. Estes vidros apresentam larga janela de transmissão (400-4500 nm), alto índice de refração (~ 1,9), baixa energia de fônon (700 cm-1), alta resistência mecânica e durabilidade química. Com a finalidade de verificar a nucleação das NPs metálicas e semicondutoras, foram realizadas análises por Microscopia Eletrônica de Transmissão (MET) que indicaram a presença de NPs metálicas e semicondutoras. As técnicas de espectroscopia de fluorescência de raios X por energia dispersiva (EDS energy dispersive spectroscopy) e difração de elétrons comprovaram a natureza química das NPs. As medidas de absorção óptica evidenciaram a incorporação dos íons de TRs na forma trivalente, fenômeno responsável pela luminescência nos vidros, e permitiram as medidas das bandas de absorção relacionadas à ressonância dos plasmons superficiais e das bandas de absorção características de NPs de natureza semicondutora. Medidas de emissão foram realizadas através de diferentes procedimentos, que variaram de acordo com a natureza das TRs. Foram medidas intensas bandas de emissão da luz vermelha do Eu3+ relacionadas com as transições 7F J (J=0 a 6) -> 5D0, bandas de emissão associadas à conversão ascendente de freqüências do Er3+ em 530, 550 e 670nm relacionadas com as transições 2H 11/2 -> 4I 15/2 , 4S 3/2 -> 4I 15/2 e 4F 9/2 -> 4I 15/2 respectivamente, e bandas de emissão de luz na região do infravermelho do Nd3+ em 900, 1076 e 1350 nm relacionadas com as transições 4F 3/2 -> 4I 9/2 , 4F 3/2 -> 4I 11/2 e 4F 3/2 -> 4I 13/2 . Foi observado aumento significativo da luminescência da luz vermelha do Eu3+ nas amostras contendo NPs de prata, ouro, e prata juntamente com ouro. Nas amostras contendo NPs de silício foi observado aumento significativo da emissão associada à conversão ascendente de freqüências do érbio. Os aumentos ocorridos na luminescência das amostras contendo NPs metálicas são provavelmente causados pelo aumento do campo local nas proximidades dos íons de TRs e pela transferência de energia entre as NPs e os íons deTRs. Os aumentos ocorridos na luminescência das amostras contendo NPs semicondutoras são provavelmente causados pela transferência eficiente de energia entre as NPs e os íons de TRs originada da recombinação de éxcitons dentro das NPs semicondutoras. Portanto, a presença das NPs desempenha um papel importante para o aumento da luminescência, permitindo o desenvolvimento de novos materiais com aplicações em nanofotônica.
This work presents a spectroscopic study about Eu3+, Nd3+ and Er3+ rare-earth doped germanate glasses containing metallic and semiconductor nanoparticles (NPs) aiming the development of new materials for photonic applications. These glasses have a large transmission window (400-4500 nm), high refractive index (~ 1.9), low phonon energy (700 cm-1), high mechanic resistance and chemical durability. Transmission Electronic Microscopy analysis was performed to verify the metallic and semiconductor NPs nucleation, and indicated the presence of metallic and semiconductor NPs. X ray fluorescence by energy dispersive spectroscopic (EDS) and electron diffraction analysis showed the chemical nature of the NPs. Optic absorption measurement proved the trivalent incorporation of the rare-earth ions, the responsible phenomenon for the luminescence of the glasses that allowed the measurement of the absorption bands related to the superficial plasmon resonance. Emission measurements were performed with different procedures, related to nature of the rare-earth. High emission bands of Eu3+ were measured related to the 7F J (J=0 to 6) -> 5D 0 transitions; emission bands associated to the frequency upconversion of Er3+ in 530, 550 and 670nm related to the 2H 11/2 -> 4I 15/2, 4S 3/2 -> 4I 15/2 e 4F 9/2 -> 4I 15/2 transitions were observed, and as well as emission bands of Nd3+ in 900, 1076 and 1350 nm related with the 4F 3/2 -> 4I 9/2, 4F 3/2 -> 4I 11/2 e 4F 3/2 -> 4I 13/2 transitions. A significant enhancement of the red light luminescence of Eu3+ was observed in the samples containing silver, gold, and silver together with gold NPs. For the samples containing silicon NPs it was observed a considerable enhancement of the frequency upconversion emission of the erbium. The luminescence enhancement of the samples with metallic NPs is due to the enhancement of the local field nearby the rare-earth ions and/or to the energy transfer between the NPs and the rare-earth ions. The luminescence enhancement of the samples with semiconductor NPs are due to the efficient energy transfer between the NPs and the rare-earth ions originated from the excitons recombination inside the semiconductor NPs. Therefore, the presence of the NPs plays an important role on the luminescence enhancement, allowing de development of new materials for nanophotonic applications.

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Pereao, Omoniyi Kolawole. "Functionalisation of electrospun nanofibre for lanthanide ion adsorption from aqueous solution." University of the Western Cape, 2018. http://hdl.handle.net/11394/6393.

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Philosophiae Doctor - PhD (Chemistry)
Rare earth elements (REEs) have widespread use and importance for industrial applications due to their metallurgical, optical and electronic properties. Several typical hydrometallurgical techniques such as adsorption, chemical precipitation, filtration, ion exchange and solvent extraction techniques have been used for separation and recovery of the rare earth metals from aqueous solutions. Adsorption was recognised as one of the most promising methods due to its simplicity, high efficiency and availability. Many adsorbents are being investigated but there are few adsorbents containing specific functional groups in practical use for REEs recovery. This aim of this study was to develop a nanofibre based adsorbent containing glycolic acid functional groups for the recovery of rare earth metals. Polystyrene (PS) and polyethylene terephthalate (PET) nanofibres were prepared by the electrospinning technique, glycolic acid functional groups were grafted onto the PS or PET nanofibres and the potential of the two modified nanofibre adsorbents for adsorption of Ce3+ or Nd3+ from aqueous solution were investigated and compared. The adsorption experiments were carried out to investigate the effect of different adsorption parameters such as pH, contact time and initial concentration in a batch system in order to achieve the objectives of this research.

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Lovrić, Marko [Verfasser], Dieter [Akademischer Betreuer] Suter, and Philippe [Akademischer Betreuer] Goldner. "Hyperfine characterisation and enhanced optical to spin storage in rare earth ion doped crystals / Marko Lovrić. Betreuer: Dieter Suter. Gutachter: Philippe Goldner." Dortmund : Universitätsbibliothek Dortmund, 2012. http://d-nb.info/1098312368/34.

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Freitas, Alysson Miranda de. "Estudo dos parâmetros de emissão laser de vidros fosfatos dopados com nanocristais de ZnTe e co-dopados com íons de Yb3+." Universidade Federal de Juiz de Fora (UFJF), 2015. https://repositorio.ufjf.br/jspui/handle/ufjf/4903.

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

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Santos, Simei Tarse Sobrinho. "Síntese e caracterização de materiais híbridos siloxano-PMMA dopados com íons Eu(III)." Pós-Graduação em Química, 2014. https://ri.ufs.br/handle/riufs/6058.

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In this work siloxane-polymethyl methacrylate (PMMA) hybrid materials were synthesized and doped with Eu (III) from solid europium chloride, solid europium (III) nitrate, europium chloride (III) in alcoholic solution and 3-aminopyrazine-2-carboxylate of lanthanum and europium complex. The hybrid was prepared from methyl methacrylate (MMA) and 3-methacryloxy-propyl-trimethoxysilane (MPTS), using benzoyl peroxide (BPO) as polymerization initiator. The use of the sol-gel method by acid catalysis allowed to obtain pure solid materials and doped with europium different sources with amorphous characteristics, as evidenced by the X-ray diffraction powderdata. The insertion of the europium complex in the polycrystalline matrix did not changethe structural characteristics of the samples. It was observed that the materials doped with europium in solution, showed greater adsorbed amounts of solvents and structural features that changethe spectroscopic properties. The samples containing solid salts showed similar structural features. It was observed that the average life time of the radioactive emissions increase with the heat treatment, indicating that the temperature reduces the number of suppressor luminescence groups in the coordinationenvironment oflanthanides ion and the character non monoexponentialof the decay is indicative of the presence different coordination environments. In the 29Si NMR measurementsfor samples containing alcoholic solution of europium chloride are observed monomer (RSi(OSi)(OH)2), diimeric(R-Si(OSi)2(OH)) and fully condensed (RSi(OSi)3)species,having a polycondensationdegree up to 78% . The materialsdoped with europium complex show strong luminescence, except tosamples treated at 200 ° C, which is indicative of thermal degradation of the coordination complex. It was observed that presence of solvent changedthermal stability, different heat treatments and europium sources exerted strong influence on the coordination environment of the Eu (III) ions in the organic -inorganic hybrid materials.
Neste trabalho materiais híbridos Siloxano-Polimetacrilato de metila (PMMA) foram sintetizados e dopados com íons Eu(III) provenientes de cloreto e nitrato de európio (III) sólidos, cloreto de európio (III) em solução alcoólica e complexo 3-aminopirazina-2-Carboxílato de lantânio e európio. O hibrido foi preparado a partir dometacrilato de metila (MMA) e do 3-metacriloxi-propil-trimetoxisilano (MPTS), utilizando-se como agente inicializador de polimerização o peróxido de benzoila (BPO). A utilização dametodologia de síntese sol-gel por catálise ácida possibilitou a obtenção de materiais sólidos puros e dopados com diferentes fontes de európio, com características amorfas, como ficou evidente pelos dados de difração de raios X de pó. A inserção de complexo de európiopolicristalino na matriz não alterou as características estruturais da amostra.Observou-se que os materiais que foram dopados com európio em solução, apresentaram maior quantidade de solventes adsorvidos e características estruturais que alteraram as suas propriedades espectroscópicas. As amostras dopadas com sais sólidos apresentaram características estruturais semelhantes. Observou-se que os tempos de vida médios das emissões radiativas aumentam com o tratamento térmico, o que indica que o tratamentoreduz o número de grupos supressores de luminescência no ambiente de coordenação do íon lantanídeo e o caráter não monoexponencial do decaimento é indicativo da presença de diferentes ambientes de coordenação. Pelo RMN do 29Si para as amostras dopadas com solução alcoólica de cloreto de európio são observadas espécies monoméricas(R-Si(OSi)(OH)2), diméricas(R-Si(OSi)2(OH)) e totalmente condensadas(R-Si(OSi)3) com um grau de policondensação de até 78%. Os materiais dopados com o complexo apresentam forte luminescência, exceto as amostras tratadas a 200°C, o que é indicativo da degradação térmica do complexo de coordenação. Observou-se que a presença de solvente alterou a estabilidade térmica das amostras, e que a diferentes tratamentos térmicos e a dopagem com diferentes fontes de európio influenciaram sensivelmente o ambiente de coordenação dos íons Eu(III) nos materiais híbridos orgânico-inorgânicos.

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Car, Benjamin. "Étude de la dynamique des spins autour d'un ion erbium pour le développement de mémoires quantiques." Thesis, Université Paris-Saclay (ComUE), 2019. http://www.theses.fr/2019SACLS251/document.

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Aux basses températures, les matrices dopées aux ions terre-rare sont des systèmes prometteurs pour la réalisation de mémoires quantiques. Parmi elles, le système Er³⁺:Y₂SiO₅ a l'avantage de posséder une transition aux longueurs d'onde Télécom, adaptée aux réseaux de communication actuels. Cependant, aucun stockage quantique n'a pu être réalisé de manière efficace durant un temps suffisamment long dans ce matériau. L'objectif de cette thèse est de mieux comprendre les interactions limitant la cohérence du système aux faibles champs magnétiques. Dans ce cadre là, les interactions dominantes sont les basculements réciproques entre deux spins électroniques opposés des ions erbium et l'interaction super-hyperfine entre ces spins et les spins nucléaires des ligands yttrium. J'ai calculé la force et les caractéristiques de ces deux couplages dipolaires en incluant la grande anisotropie de la matrice Y₂SiO₅. J'ai alors pu vérifier l'effet de cette anisotropie sur les basculements réciproques des spins des ions erbium à l'aide de deux techniques optiques, le creusement de trou spectral et l'excitation transitoire. Le taux de ces basculements est maximisé lorsque le champ magnétique est orienté perpendiculairement à l'axe principal du tenseur caractérisant le spin effectif. Il augmente globalement comme le carré de la concentration en ions dopants et diminue avec le champ magnétique. Enfin, j'ai pu mesurer les caractéristiques des interactions super-hyperfines par le biais des modulations d'une décroissance d'écho de photon qu'elles provoquent. Il existe une configuration particulière où un couplage sélectif intervient entre les ions erbium et un unique yttrium de leurs environnements. Au contraire, le couplage à un nombre important d'ions ligands est responsable de la chute du temps de cohérence pour des champs magnétiques inférieurs à la dizaine de mT
At low temperatures, rare-earth doped matrices are promising supports for the development of quantum memories. Among them, Er³⁺:Y₂SiO₅ is well adapted to the current communication networks because of its transition at Telecom wavelength. However, quantum storage has a very limited efficiency and a short duration in this material. In this thesis, I study the interactions that hinder the coherence at low magnetic fields. In this regime, the dominant processes are flip-flops between opposite electronic spins of erbium ions and the super-hyperfine interaction with nuclear spins of yttrium ligands. I have included the strong anisotropy of the Y₂SiO₅ matrix in the calculation of these two dipolar interactions. In order to check the anisotropy of the flip-flops between erbium spins, I have used two different optical techniques : spectral hole-burning and transient excitation. I have showed that their rate is maximum when the magnetic field is perpendicular to the principal axis of the effective spin tensor. Moreover, the flip-flop probability globally increases as the square of the doping concentration and as the inverse of the field. Then I have also checked the calculations of super-hyperfine interactions by measuring photon echo modulations. I have found a particular situation where an erbium ion is strongly coupled to a single yttrium. On the contrary, the coupling to several ligands at very low magnetic fields drastically reduces the coherence time

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Cordeiro, Neto Marcelino. "Espectroscopia óptica dos vidros PZABP dopados com terras-raras e nanopartículas semicondutoras." Universidade Federal de Juiz de Fora (UFJF), 2014. https://repositorio.ufjf.br/jspui/handle/ufjf/5356.

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CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
O objetivo desta tese é analisar se as propriedades ópticas apresentadas neste trabalho qualiﬁcam o sistema vítreo PZABP, com composição nominal 60P2O5.15ZnO.5Al2O3.10BaO.10PbO (% mol), dopado com íons terras-raras trivalentes, itérbio (Yb3+) e európio (Eu3+) e, também, com nanopartículas semicondutoras de telureto de zinco (ZnTe) como potencialmente útil para construção de dispositivos de emissão de luz na região de 920 nm a 1060 nm. A teoria de Judd-Ofelt é usada nos cálculos dos parâmetros de intensidade Ωλ(λ = 2,4,6). Técnicas de microscopia de força atômica (AFM), absorção óptica (AO), fotoluminescência (FL) e fotoluminescência resolvida no tempo (FLRT) caracterizam o sistema vítreo. A ﬁnalidade do ZnTe é aumentar a seção de choque de absorção do sistema vítreo PZABP e transferir energia para os íonsEu3+ e/ouYb3+. A formação de dois tipos de nanopartículas semicondutoras de telureto de zinco ZnTe-propriedades de bulk e pontos quânticos – foram identiﬁcados. FL e FLRT sugerem transferência de energia dos íons de Eu3+ e/ou ZnTe para os íons deYb3+.
The aim of this thesis is to analyze if the optical properties presented in this work qualify the glass system PZABP, with nominal composition 60P2O5.15ZnO.5Al2O3.10BaO.10PbO(% mol), doped with trivalent rare earth ions, ytterbium (Yb3+) and europium (Eu3+) as well as zinc telluride (ZnTe) as potentially useful for light emission devices in the infrared region from 920 nm to 1060 nm. The Judd-Ofelt theory is used to calculate the intensity parameters Ωλ(λ = 2,4,6). Atomic force microscopy (AFM), optical absorption (OA), photoluminescence (PL) and time-resolved photoluminescence (TRPL) techniques characterized the vitreous system. The formation of two kinds of ZnTe semiconductor nanoparticles - bulk-like and quantum dots –were identiﬁed. PL and TRPL suggest the energy transfer from Eu3+ ions and/orZnTetoYb3+ ions.

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Queiroz, Thiago Branquinho de. "Caracterizações estruturais e espectroscópicas de cerâmicas ferroelétricas de PLZT dopadas com íons de terras raras trivalentes." Universidade de São Paulo, 2009. http://www.teses.usp.br/teses/disponiveis/76/76131/tde-10032009-111852/.

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Recentemente, grande interesse tem sido demonstrado por cerâmicas transparentes dopadas com íons terras raras trivalentes, como meios ativos para lasers na região espectral do infravermelho próximo. Em particular, cerâmicas dopadas com altas concentrações de Nd3+ e Yb3+ são muito estudadas pela possibilidade de gerar emissão laser de alta potência em torno de 1,0 mm. Embora a cerâmica transparente de titanato zirconato de chumbo e lantânio (PLZT), com composição La/ Zr/Ti = 9/65/35, seja originalmente reconhecida por suas propriedades ferroelétricas e eletro-ópticas, a mesma também apresenta características interessantes como matriz hospedeira de íons oticamente ativos. Recentemente, de Camargo et al. realizaram vários estudos espectroscópicos que comprovam a potencialidade laser de amostras dopadas com Yb3+, Er3+, Tm3+ e em especial Nd3+. Apesar de a cerâmica PLZT:Nd ser a mais promissora, se comparada a líder de mercado YAG:Nd (sistema ítrio-alumínio garnet dopado com neodímio), ainda não foi possível obter ação laser da primeira, devido à presença de fases espúrias (imperceptíveis a olho nu), que comprometem a qualidade óptica do material, especialmente para concentrações de dopagem maiores que 1,0% peso de Nd2O3. Uma vez que a qualidade estrutural tem implicação direta na qualidade óptica/espectroscópica de materiais ópticos, faz-se necessário estender os estudos visando otimizar a obtenção de amostras transparentes com mais altos níveis de dopagem. Neste trabalho apresenta-se um método alternativo para a dopagem da matriz PLZT com os íons TR = Nd3+ e Yb3+, e utiliza-se de várias técnicas (DR-X, DTA-TG, FT-IR, Raman, RMN e Luminescência), para caracterizar os compostos precursores e/ou produtos. O novo método baseia-se na obtenção prévia de óxidos precursores dopados, seguida da utilização destes para o preparo das cerâmicas PLZT:TR. As caracterizações foram conduzidas em função da concentração de dopantes (0,1 4,0% peso TR2O3), comparativamente ao método de dopagem convencional utilizado nos trabalhos anteriores. A espectroscopia de ressonância magnética nuclear em sólidos em 207Pb, mostrou-se uma ferramenta bastante útil na elucidação de questões estruturais desses sistemas tão complexos. Como os íons paramagnéticos Nd3+ e Yb3+ não podem ser diretamente acessados por RMN, a estratégia para caracterizar suas distribuições espaciais foi investigar suas respectivas mímicas diamagnéticas Y3+ e Sc3+ (núcleos 45Sc e 89Y). Resultados de DR-X apresentam menor formação de fase secundária nas amostras preparadas via método alternativo, sendo identificado as fases secundárias como (La,Nd)2(Zr,Ti)2O7 (estrutura do tipo pirocloro), ZrO2 em fase parcialmente monoclínica e cúbica e ZrO2 em fase cúbica, das amostras dopadas com Nd3+, Y3+ e Yb3+, respectivamente. De acordo com os resultados de DR-X, experimentos de RMN permitiram melhor avaliação quanto a inserção do íon dopante a medida que há formação de fase secundária e mostraram que a inserção dos íons dopantes é homogênea, bem como resultados de luminescência, com o limite de solubilidade do íon dopante sempre menor do que o necessário para que seja observado supressão da luminescência dos íons emissores.
In recent years, there has been a great interest for rare-earth (RE) doped transparent ceramics as near-infrared laser active media. Particularly, Nd3+ and Yb3+-doped ceramics are of special interest due to the possibility of generating high power emissions at around 1.0 mm. Even though lead lanthanum zirconate titanate (PLZT) ceramics, with composition La/Zr/Ti = 9/65/35, are mostly known by their ferroelectric and electro-optic properties, recent works by de Camargo et al. have also indicated their potentiality as laser active media. In this regard, the most promising system is PLZT:Nd (as compared to YAG:Nd - neodymium-doped yttrium aluminium garnet), however, laser action of the former has not yet been possible, the reason lying in the presence of secondary phases (invisible to the naked eye) that compromise the optical quality of the ceramics, especially for samples with concentration higher than 1.0 wt% Nd2O3. Since the structural quality of samples has a direct implication on their spectroscopic and optical qualities, the goals pursued in this work are to present means to obtain highly transparent samples with higher incorporation of dopants, as well as to understand some fundamental questions regarding the microstructure of PLZT:RE ceramics. Thus, an alternative method, based on the obtainment of RE-doped precursor oxides, is presented for the synthesis of PLZT:RE and several techniques (XRD, DTA-TG, FT-IR, Raman, NMR and Luminescence) are used to characterize the samples, as a function of doping concentration (0,1 4,0 wt% RE2O3). These studies are done in comparison to the conventional method used in previous works. Solid state NMR spectroscopy of 207Pb proved to be a very useful tool for the understanding of these complex systems. Because Nd3+ and Yb3+ are paramagnetic and thus inaccessible by NMR, the strategy used for the characterization of their spatial distribution was to study samples doped with their respective diamagnetic mimics Sc3+ and Y3+ (45Sc and 89Y nuclei). XRD results have shown formation of less secondary phase for samples prepared by alternative method, being identified as secondary phase pyrochlore structure (La,Nd)2(Zr,Ti)2O7, partially monoclinic/cubic ZrO2 and cubic ZrO2 of the samples doped with Nd3+, Y3+ and Yb3+ respectively. NMR measurements allowed to make proposals about dopant ion insertion while secondary phase is formed and showed homogeneous distribution of dopant into the matrix, aswell luminescence measurements with maximum dopant solubility being less than enough to show any suppression of luminescence.

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29

Wang, Wei. "Computational Spectroscopic Analysis of Orbital Hybridization and Crystal Field Interaction for Trivalent Uranium Ion in Crystals of Hexagonal Symmetry." University of Cincinnati / OhioLINK, 2009. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1258479110.

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30

Mhibik, Oussama. "Développement des sources lasers solides continues, visibles et stabilisées en fréquence : une alternative aux lasers à colorants." Phd thesis, Université Paris Sud - Paris XI, 2011. http://tel.archives-ouvertes.fr/tel-00656426.

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Le traitement de l'information quantique, en particulier celui utilisant les centres colorés du diamant et la manipulation cohérente des ions de terre rare incorporés dans des matrices solides (Pr3+, Eu3+) et la spectroscopie à ultra-haute résolution, nécessitent des sources accordables ayant une faible largeur de raie. Or, dans la gamme rouge-orange (570-635 nm) où les diodes lasers font défaut et les lasers solides restent très peu développés, les lasers à colorants sont actuellement les seules sources de rayonnement cohérent disponibles. En revanche, ce type de laser est assez complexe et difficile à stabiliser au niveau du kHz à cause des bruits à haute fréquence générés par le jet de colorant.Pour répondre aux besoins des expériences citées ci-dessus, cette thèse vise à proposer une alternative "tout solide" aux lasers à colorants en explorant différentes possibilités pour la construction d'une source stable émettant dans l'orange-rouge. Dans ce but, nous avons proposé deux solutions:1. La première consiste à développer des oscillateurs paramétriques optiques. Dans cette voie, nous avons développé un OPO simplement résonant à doublage de fréquence intra-cavité et stabilisé en frequence au niveau du kHz.2. La deuxième consiste en un laser à base de fluorures dopés au Pr3+pompé par diode.

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QUEIROZ, CARLOS A. da S. "Terras raras: fracionamento, purificação e controle analítico." reponame:Repositório Institucional do IPEN, 1988. http://repositorio.ipen.br:8080/xmlui/handle/123456789/11634.

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Dissertacao (Mestrado)
IEA/D
Instituto de Quimica, Universidade de Sao Paulo - IQ/USP

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FUJIMOTO, TALITA G. "Microestrutura e propriedades elétricas e dielétricas do titanato de estrôncio puro e contendo aditivos." reponame:Repositório Institucional do IPEN, 2016. http://repositorio.ipen.br:8080/xmlui/handle/123456789/26933.

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O titanato de estrôncio (SrTiO3) possui estrutura cristalina do tipo perovsquita. Materiais com este tipo de estrutura são utilizados para diversas aplicações, tais como, sensores, atuadores, em células a combustível de óxido sólido, entre outros. Devido as suas interessantes propriedades físicas, o SrTiO3 vem sendo intensamente estudado, em especial com a introdução de dopantes. Portanto, neste trabalho foi investigada a influência de diferentes teores de Ca (1; 2,5 e 5% mol) e Pr (0,025; 0,050; 0,075 e 1% mol) na microestrutura e propriedades elétricas e dielétricas do SrTiO3, assim como o material sem aditivos (puro). Os resultados mostram que após a sinterização do SrTiO3 puro, a microestrutura consiste de grãos poligonais com tamanho médio micrométrico, além de texturas lisas e rugosas. A condutividade elétrica das amostras sintetizadas sinterizadas a 1450 e 1500ºC é máxima para 2 horas de patamar. Apenas as amostras de SrTiO3 contendo 1% em mol de Ca apresentam fase única. O tamanho médio de grãos das amostras contendo 1% em mol de Ca é 10,65 ± 0,28 µm e para teores acima deste valor ocorre crescimento significativo dos grãos. As medidas de condutividade elétrica mostraram que as amostras contendo a adição de 1% em mol de Ca possuem maior condutividade dos grãos em relação ao material puro. Para as amostras contendo teores de até 0,075% mol de Pr, pode-se observar alguns grãos lisos e outros rugosos e não há variação considerável do tamanho médio de grãos. As amostras contendo menor teor de Pr (0,025% mol) apresentam maior condutividade dos grãos e contornos de grãos. As amostras de SrTiO3 sintetizado sinterizadas a 1450ºC/10 h apresentaram permissividade elétrica colossal em temperatura ambiente em altas frequências.
Dissertação (Mestrado em Tecnologia Nuclear)
IPEN/D
Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

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33

Magne, Sylvain. "Etat de l'art des lasers à fibre : étude d'un laser à fibre dopée ytterbium et spectroscopie laser de fibres dopées." Saint-Etienne, 1993. http://www.theses.fr/1993STET4027.

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Cette thèse montre l'intérêt de l'amplification optique et des lasers à fibres dopées par des ions de terres-rares pour l'instrumentation et les capteurs à fibres optiques. Nous détaillons les avantages et les inconvénients d'une telle technologie placée dans son contexte d'optique intégrée, ainsi que ses perspectives d'utilisation. Apres rappel de la théorie de la propagation guidée dans les fibres optiques, les technologies permettant de réaliser des fibres optiques dopées sont décrites. Une étude comparative des méthodes d'analyses de préformes et de fibres dopées permettant de déterminer leurs profils de guidage et de dopage est également présentée. Le comportement amplificateur des fibres optiques dopées est ensuite décrit théoriquement en insistant sur les limites fixées par l'élargissement inhomogène de la transition laser. L'évolution du gain intégré de la fibre est mise en évidence en fonction des paramètres influants (longueur, rayon de dopage. . . ) en soulignant l'intérêt d'un rayon de dopage optimisé. Le seuil d'accrochage du laser est modélisé par des équations et des abaques sans dimension déterminant la longueur de fibre optimale en fonction des pertes de la cavité laser. La conception générale du laser à fibre est ensuite synthétisée et les technologies des composants d'optique intégrée adaptés à la fibre amplificatrice le constituant sont comparées. Les techniques expérimentales concernent principalement l'étude de l'accordabilité par excitation sélective de sites et de la limitation du gain par émission stimulée sur la transition de pompage induisant une absorption résiduelle non saturable ; l'étude des effets de transferts dans les fibres dopées par luminescence coopérative : l'étude d'un procédé de changement de valence par irradiation y conduisant à une réduction des ions uranium placés en matrice verre fluoré (zblan) ; la démonstration d'un effet laser à trois niveaux, fonctionnant en régime continu et en contre-réaction externe par réseau

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Longdell, J. "Quantum Information Processing in Rare Earth Ion Doped Insulators." Phd thesis, 2003. http://hdl.handle.net/1885/47689.

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A great deal of theoretical activity has resulted from blending the fields of computer science and quantum mechanics. Out of this work has come the concept of a quantum computer, which promises to solve problems currently intractable for classical computers. This promise has, in turn, generated a large amount of effort directed toward investigating quantum computing experimentally. ¶ Quantum computing is difficult because fragile quantum superposition states of the computer’s register must be protected from the environment. This is made more difficult by the need to manipulate and measure these states. ¶ This thesis describes work that was carried out both to investigate and to demonstrate the utility of rare earth ion dopants for quantum computation. Dopants in solids are seen by many as a potential means of achieving scalable quantum computing. Rare earth ion dopants are an obvious choice for investigating such quantum computation. Long coherence times for both optical and nuclear spin transitions have been observed as well as optical manipulation of the spin states. The advantage that the scheme developed here has over nearly all of its competitors is that no complex nanofabrication is required. The advantages of avoiding nano-fabrication are two fold. Firstly, coherence times are likely to be adversely effected by the “damage” to the crystal structure that this manufacture represents. Secondly, the nano-fabrication presents a very serious difficulty in itself. ¶ ...

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Yan, Kunlun. "Rare-earth ion doped chalcogenide waveguide amplifiers." Phd thesis, 2018. http://hdl.handle.net/1885/162514.

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Chalcogenide glass waveguide devices have received a great deal of attention worldwide in the last few years on account of their excellent properties and potential applications in mid-infrared (MIR) sensing and all-optical signal processing. Waveguide propagation losses, however, currently limit the potential for low power nonlinear optical processing, and the lack of suitable on chip integrated MIR sources is one of the major barriers to integrated optics based MIR sensing. One approach to overcome the losses is to employ rare-earth ion doped waveguides in which the optical gain can compensate the loss, in such a way that the conversion efficiency of nonlinear effects is increased significantly. For infrared applications, the long wavelengths potentially attainable from rare-earth ion transitions in chalcogenide hosts are unique amongst glass hosts. New rare-earth ion doped chalcogenide sources in the MIR range could benefit molecular sensing, medical laser surgery, defence etc. Despite these promising applications, until now, no one has succeeded in fabricating rare-earth ion doped chalcogenide amplifiers or lasers in planar devices. This work develops high quality erbium ion doped chalcogenide waveguides for amplifier and laser applications. Erbium ion doped As2S3 films were fabricated using co-thermal evaporation. Planar waveguides with 0.35 dB/cm propagation loss were patterned using photolithography and plasma etching on an erbium ion doped As2S3 film with an optimised erbium ion concentration of 0.45x1020 ions/cm3. The first demonstration of internal gain in an erbium ion doped As2S3 planar waveguide was performed using these waveguides. With different film deposition approaches, promising results on intrinsic lifetime of the Er3+ 4I13/2 state were achieved in both ErCl3 doped As2S3 films (2.6 ms) and radio frenquency sputtered Er3+:As2S3 films (2.1 ms), however, no waveguide was fabricated on these films due to film quality issues and photopumped water absorption issues. The low rare-earth ion solubility of As2S3 is considered the main factor limiting its performance as a host. Gallium-containing chalcogenide glasses are known to have good rare-earth ion solubility. Therefore, a new glass host material, the Ge-Ga-Se system, was investigated. Emission properties of the bulk glasses were studied as a function of erbium ion doping. A region between approximately 0.5 and 0.8 at% of Er3+ ion was shown to provide sufficient doping, good photoluminescence and adequate lifetime to envisage practical planar waveguide amplifier devices. Ridge waveguides based on high quality erbium ion doped Ge-Ga-Se films were patterned. Significant signal enhancement at 1540 nm was observed and 50 % erbium ion population inversion was obtained, in waveguides with Er3+ concentration of 1.5x1020 ion/cm3. To the Author's knowledge, this is the highest level of inversion ever demonstrated for erbium ions in a chalcogenide glass host and is an important step towards future devices operating at 1550 nm and on the MIR transitions of erbium ions in chalcogenide glass hosts. Photoinduced absorption loss caused by upconversion products in the waveguides is the remaining hurdle to achieving net gain. Further research is needed to find suitable compositions that possess high rare-earth ion solubility whilst avoiding the detrimental photoinduced losses.

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36

Cho, Junghyun. "Role of rare-earth dopants on the improved creep properties of aluminum oxide /." Diss., 1998. http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqdiss&rft_dat=xri:pqdiss:9919142.

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37

Tissue, Brian Max. "Energy transfer in rare earth ion clusters and fluorescence from rare earth doped La₁ ̣₈₅Sr₀ ̣₁₅CuO₄ superconductors." 1988. http://catalog.hathitrust.org/api/volumes/oclc/20189246.html.

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38

Bartholomew, John Glen. "Investigation of the scalability of rare-earth-ion quantum hardware." Phd thesis, 2014. http://hdl.handle.net/1885/150124.

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In the last decade, the solid-state rare-earth-ion system has demonstrated increasing appeal for quantum computation. Despite this progress, two hardware limitations prevent a scalable implementation. These current limitations are the inability to miniaturise and the inability to perform single-ion qubit readout. This thesis addresses both these limitations and demonstrates that neither poses a fundamental restriction on increasing the scale of rare-earth-ion quantum computers. The challenge in miniaturising rare-earth-ion quantum hardware arises from the increases in homogeneous and inhomogeneous broadening that accompany micron-scale architectures. The success of miniaturised architectures, such as waveguides, depends on the properties of bulk ions being preserved within microns of the crystal surface. In addition, bulk ion properties must also be preserved in regions of high residual stress resultant from waveguide fabrication. The inhomogeneous and homogeneous properties of near-surface ions and ions in highly stressed environments in Pr3+:Y2SiO5 were studied via white light interferometry combined with micron resolution fluorescence microscopy. It was found that the bulk ion properties could be preserved both near the surface and in highly stressed regions close to micron-scale surface damage. The observation of excess inhomogeneous and homogeneous broadening was found to be consistent with the damage present at the crystal surface. The main outcome of the study was a set of waveguide fabrication guidelines to ensure that the appealing properties of bulk crystals can be maintained in a miniaturised architecture. The current inability to perform single-ion qubit readout is a consequence of the difficulty in isolating a single ion and lack of cyclicity in rare-earth-ion materials. Two techniques are proposed to form a solution: Stark activation and Zeeman enhanced cyclicity. When combined, these techniques offer direct readout for single-ion frequency-based quantum computing. Stark activation is designed to isolate a single rare-earth ion in a macroscopic crystal. The proposal is based on defining the condition for resonant excitation through a spatially varying electric field. A proof-of-principle experiment successfully created a 10 um absorption region within a millimetre thick crystal. In addition, the signal-to-noise ratio of the technique was characterised in experiments probing Pr3+:Y2SiO5 at the single-ion level. Future improvements to the apparatus should allow the nanometre spatial resolution and the noise level to be reduced to allow single-ion optical detection. High cyclicity is essential for high-fidelity optical readout of a single-ion qubit. Zeeman enhanced cyclicity achieves this by manipulating the hyperfine structure of the resonant crystal field levels to induce strong hyperfine selection rules. The technique is shown to be applicable to even the lowest symmetry sites. The simulated level of cyclicity in Pr3+:Y2SiO5 was greater than 99.99% by applying a 10 T field. The investigation of scalability in the rare-earth-ion system marks a movement away from the traditional ensemble-based methods in macroscopic crystals. This study required an understanding of these materials at a single-ion level and the development of high spatial resolution spectroscopic techniques. These advances extend the ability to engineer rare-earth-ion systems for applications including, but not limited to, quantum computing.

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39

Marzban, Sara. "Rare-earth ion doped planar waveguides for integrated quantum photonics." Phd thesis, 2017. http://hdl.handle.net/1885/144606.

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This thesis presents a spectroscopic study of Pr3+ ions in a novel passive waveguide architecture. To make this structure, the high refractive glass TeO2 was selected as the thin film and it was deposited on a Pr3+:Y2SiO5 crystal. In this waveguide, the 3H4 to 1D2 transition of Pr3+ ions were probed by the optical evanescent field extending into the substrate. The main concern in assessing the suitability of this material for quantum information applications was ensuring that the coherence properties of rare-earth ions, making them suitable for quantum information purposes, are preserved in this architecture. After which, to make low loss devices with these waveguides, efficient coupling techniques had to be developed. To prove that the coherence properties of the rare-earth ion doped crystal were preserved, the critical parameters of inhomogeneous linewidth, the absorption of the ions, the coherence time and spin lifetimes of the Pr3+ ions were studied. The inhomogeneous linewidth of evanescent coupled ions was about 10.0 GHz, which was consistent with the linewidth of bulk samples with the same Pr3+ doping concentration (Hedges, 2011). The absorption due to the evanescent coupling was 9.38 dB, approximately 90% of what was expected with respect to the bulk crystal with the same doping concentration. Therefore, despite using the evanescent field, the absorption is high enough for quantum memory applications. An optical coherence time of about 121 microseconds was measured, which corresponded to a homogeneous linewidth of about 2.6 kHz. This is very close to bulk sample measurements of 111 microseconds, with the same temperature and doping concentration (R. W. Equall, 1995). The spin state lifetime observed was about 9.8 s, which is also very close to the bulk sample measurement of 8.67 s (Mieth, 2016). Initial Stark shifting experiments were performed to determine whether the active ions in the substrate of the passive waveguides could be electrically controlled by applying a small voltage to electrodes on the thin film. In these experiments with a voltage change of 100 mV, the measured holewidth broadening was increasing about 0.55 MHz, which was similar to the calculated values of 0.45 MHz. The Stark coefficient for site 1 was 51.6 kHzcm/V along the D2 axis of the crystal (site 1 will be explained in Section 4.3). (F.R. Graf, 1997). Prism coupling and grating coupling were used to couple light to the ions in the substrate. Prism coupling is an easy and quick method to couple light into a waveguide and observe the properties of the system. However, grating coupling is much more practical when moving towards building a device using this method. The measurements described above indicated that the properties of ions interacting with the evanescent tail of the waveguide mode were consistent with those of bulk ions. This investigation also showed that depositing a glass thin film on a rare-earth ion doped crystal was not affecting the good coherence properties of the substrate. These results establish the foundation for large, integrated, controllable and high performance rare earth ion quantum waveguide systems.

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40

Fraval, Elliot. "Minimising the Decoherence of Rare Earth Ion Solid State Spin Qubits." Phd thesis, 2005. http://hdl.handle.net/1885/47058.

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This work has demonstrated that hyperfine decoherence times sufficiently long for QIP and quantum optics applications are achievable in rare earth ion centres. Prior to this work there were several QIP proposals using rare earth hyperfine states for long term coherent storage of optical interactions. The very long T_1 (~weeks ) observed for rare-earth hyperfine transitions appears promising but hyperfine T_2s were only a few ms, comparable to rare earth optical transitions and therefore the usefulness of such proposals was doubtful. ¶ This work demonstrated an increase in hyperfine T_2 by a factor of 7 × 10^4 compared to the previously reported hyperfine T_2 for Pr^[3+]:Y_2SiO_5 through the application of static and dynamic magnetic field techniques. This increase in T_2 makes previous QIP proposals useful and provides the first solid state optically active Lamda system with very long hyperfine T_2 for quantum optics applications. ¶ ...

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41

Han-LinHsu and 徐漢霖. "Synthesis and luminescent properties of rare-earth ion doped Li3Ba2La3(MoO4)8 phosphors." Thesis, 2010. http://ndltd.ncl.edu.tw/handle/42024449184955709194.

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碩士
國立成功大學
材料科學及工程學系碩博士班
98
Rare-earth (RE) ion doped phosphors, Li3Ba2La3-xREx(MoO4)8 (RE = Eu3+, Dy3+), were synthesized by a solid-state reaction process at 800C. The structural and photoluminescent properties of the prepared phosphors were investigated by X-ray diffraction, scanning electron microscopy, Raman scatter spectroscopy, UV-visible absorption, and photoluminescence (PL) spectroscopy. The aim of the research was to develop novel phosphors for the UV-LED to white light conversions. The experimental results showed that the dominant emissions of the Li3Ba2La3-xEux(MoO4)8 phosphors under the UV excitation (394 nm) were at 593 nm and 618 nm, originating from the electronic transitions between the trivalent RE states. Due to the high phonon frequency of the host lattice, the transitions from the emitting levels higher than 5D0 were not observed in the PL spectra. The above two observed emissions were due to the 5D0-＞7F1 (593 nm) and 5D0-＞7F2 (618 nm) transitions. In particular, the 5D0-＞7F2 emission was very strong and for the x=2.1 samples, its peak intensity was about 3.3 times more than the commercial phosphors ZnS:(Mn2+,Te2+). The CIE chromaticity coordinate of the Li3Ba2La0.9Eu2.1(MoO4)8 red emissions was calculated to be at (0.67, 0.33), which is almost the same as the standard red chromaticity of the NTSC system. In the Li3Ba2La3-xDyx(MoO4)8 (x=0.01-0.24) series, the dominant emissions under the UV excitation (388 nm) were from the 4F9/2-＞6H15/2 (blue) and 4F9/2-＞6H13/2 (yellow) transitions, and the intensity of the later was stronger. The mixture of all the emissions had the CIE chromaticity coordinates at (0.35, 0.40), which is at the yellowish-white color region.

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42

Thiel, Charles Warren. "Energies of rare-earth ion states relative to host bands in optical materials from electron photoemission spectroscopy." 2003. http://etd.lib.montana.edu/etd/2003/thiel/ThielC03.pdf.

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43

Chang, Yee-Cheng, and 張翌誠. "Synthesis and photo-luminescence properties of rare earth ion doped Li3Ba2Gd3(MoO4)8 phosphors." Thesis, 2009. http://ndltd.ncl.edu.tw/handle/03947122628165768871.

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碩士
國立成功大學
材料科學及工程學系碩博士班
97
The objet of this study is to synthesize Li3Ba2Gd3(MoO4)8 doped with various activators(Eu3+,Tb3+,Dy3+,Er3+,Sm3+), and the raw material had been mechanically activated by grinding in high energy vibromill followed by calcined at temperature of 900℃ for 12 h. By using XRD, SEM, PL spectra, and UV-visable spectra, the characterization of structure, morphology of powders and photo-luminescent properties of phosphors were analized. The dominant emission peaks of Li3Ba2Gd3(MoO4)8:Eu3+ phosphor are 5D0→7F1(591nm)、5D0 →7F2(614nm) which are originate from intra-4f transitions of excited state. The intensity of the emission from 5D0 to 7F2 is stronger than 5D0 to 7F1 and three times more than commercial phosphors, ZnS:Mn2+,Te2+ when Eu3+ concentration in x=2.4. The CIE chromaticity coordinates of red emission of the Li3Ba2Gd0.6Eu2.4(MoO4)8 phosphor is (0.67, 0.33) which is just at NTSC system standard red chromaticity. There are two regions in the excitation spectra of Li3Ba2Gd2 Tb1(MoO4)8 phosphor；one is assigned from 4f��5d transition in 200 to 300 nm, and the others are from intra-4f transitions in 350 to 500 nm. The dominant emission peak of Li3Ba2Gd2Tb1(MoO4)8 phosphor is 5D4��7F5 under excitation of 307nm. The CIE chromaticity coordinates of green emission of the Li3Ba2Gd2 Tb1(MoO4)8 phosphor is (0.25, 0.58). The the other series of green phosphor is Li3Ba2Gd2.95Er0.05(MoO4)8.Because its emission peaks locates in the light of green region, it has better color rendering index than Li3Ba2Gd2 Tb1(MoO4)8. However, the valence electrons are shielded by the 5s and 5p outer electrons, the valance electrons of trivalent rare earth ions are weakly affected by ligand ions in crystals, so the features of optical spectra of the most phosphors doped with trivalent rare earth, such as Li3Ba2Gd3(MoO4)8:Dy3+ and Li3Ba2Gd3(MoO4)8:Sm3+ is similar to those expected for free ions.

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44

Chen, Hou-Ren, and 陳厚仁. "Passive Mode Locking of Rare-Earth Ion Doped and Semiconductor Optical Amplifier Based Lasers." Thesis, 2013. http://ndltd.ncl.edu.tw/handle/93059022344171104008.

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博士
國立交通大學
光電工程研究所
101
In the thesis, we investigate two topics. First, we use a new fabrication method for single-walled carbon nanotube (SWCNT) and graphene oxide (GO) saturable absorbers (SAs) to sustain high-power illumination. Using a series of SAs incorporating different amounts of SWCNTs and GOs, we demonstrate mode-locking for Nd:GdVO4 and Nd:LuVO4 lasers in the 1 μm spectral range. Using SWCNT-SAs for Nd:GdVO4 laser, continuous-wave mode-locking (CWML) with a maximum output power of 3.6W at 1063 nm and high noise extinction of 61 dB has been achieved to give the highest pulse peak power of 3.6 kW and pulse energy of 30 nJ under 15-W pumping. For Nd:LuVO4 laser, GOSAs are used and CWML pulses with maximal output power of 3.89 W at 1065.7 nm are obtained under 15-W pumping to give the highest pulse peak power of 5.44 kW and pulse energy of 32 nJ, for which the high noise extinction of 66 dB has been achieved. To our knowledge, those are the highest reported output power for CWML lasers with SWCNT-SAs and GO-SAs, respectively. The measured nonlinear absorption of the SWCNT-SAs shows a modulation depth of ~3% with subpicosecond recovery time of ~630 fs. For GOSAs, the nonlinear absorption shows the modulation depth of about 2.54%, 4.14%, and 5.36% for GO amounts of 0.6, 0.9, and 1.25 mg. On the other hand, in order to insert the GOSAs between two fiber connectors, we fabricate the polymer-based GOSAs to be use in the all fiber laser system. Broadband graphene oxide/PVA films, which are used as saturable absorbers in the mode locking of erbium-doped and ytterbium-doped fiber lasers, have been demonstrated. They provide modulation depths of 2.95% and 6% at 1.06 μm and 1.55 μm, respectively. Stable self-starting mode-locked pulses are obtained for both lasers, confirming that graphene oxide does not have wavelength selectivity and is cost effective for 1.06-μm and 1.55-μm pulse generations. Second, we report the generation of passively harmonic mode-locked pulses using a 1.06 μm semiconductor optical amplifier (SOA) in a figure-eight laser configuration operated in the all-normal-dispersion regime. Different orders of harmonic mode locking can be obtained from 30 MHz to 12.02 GHz by tuning the injection current of the SOA from 80 to 660 mA together with the adjustment of polarization controllers. The highest pulse repetition rate increases almost linearly with the SOA current. As SOA current is set to 660 mA, we obtain the intracavity power of 46 mW at the highest repetition rate of 12.02 GHz, corresponding to the 1202th harmonic of the fundamental mode locking frequency. To our best knowledge, this is the lowest intracavity power to generate the highest repetition rate with a passively mode-locked laser in the all-normal-dispersion regime.

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45

(6624245), Angel A. Pena. "Evaluation of Rare-Earth Element Dopants (Sm and Er) Effect on the Ablation Resistance and Emittance Tailoring of ZrB2/SiC Sintered Billets." Thesis, 2019.

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Hypersonic flight causes ultra-high surface temperatures which are most intense on sharp leading edges. One way of reducing the surface temperature is to apply a high emittance ceramic (HEC) on the leading edge, increasing the radiation component of heat transfer. An ideal HEC must have a high emittance, while also possessing a strong ablation resistance. From a scientific standpoint, it would be helpful if emittance could be tailored at different wavelengths. For example, materials with tailorable emittance could be used to improve the efficiency of engines, thermo-photo voltaic cells, and other applications. The approach used to create a ceramic with tailorable emittance was to use two different rare-earth elements, adding them to an ultra-high temperature ceramic (UHTC) in small quantities. The samarium element was added to increase the emittance of the UHTC over a large wavelength range (visible to near infrared wavelengths, consistent with the temperature range expected for hypersonic flight), and the erbium element was added to decrease the emittance at specific wavelength ranges. The goal of this study was to create an UHTC with tailorable emittance while maintaining the required ablation resistance. Therefore, ZBS billets with five different Sm to Er ratios and with a nominal total amount of 3 mol.% dopant incorporated were prepared by sintering in vacuum to 2000 °C. The ablation resistance was evaluated by using an oxyacetylene torch and observing at exposure times of 60 s and 300 s, whereas the emittance was evaluated at the Air Force Research Lab facilities via a laser heating testing. The results for the ablation testing showed that ZrB₂-SiC (ZBS) billets co-doped with Sm and Er formed a beneficial c₁-(Sm/Er)_0.2Zr_0.8O_1.9 oxide scale as the majority phase, which is more thermally stable than the m-ZrO₂ oxide scale typically formed in oxidized ZBS systems, resulting in a more adherent oxide scale to the unreacted material. The crystalline oxide scale and the amorphous phase were formed by a convection cell mechanism where the c₁-(Sm/Er)_0.2Zr_0.8O_1.9 crystalline islands precipitate, grow, and coalesce. Moreover, differences in surface temperatures between ZBS samples with different dopant ratios suggest differences in spectral absorptance/emittance between each of the five compositions evaluated. Despite that the emittance profiles with varying Sm:Er molar ratios were similar because m-ZrO₂ was formed as the major oxide phase, the emittance study showed that the erbium oxide influences the emittance profile, as can be noted by the maximum and minimum emittance peaks. Furthermore, results showed that the emittance varies as a function of dopant(s) molar ratios and temperature at shorter wavelength ranges. These changes in the emittance are caused by the different Sm and Er concentration on the surface. Future work should be focused on producing the beneficial c₁-(Sm/Er)_0.2Zr_0.9O_1.8phase directly from the manufacturing process, and therefore, maximize the effect of varying the Sm:Er molar ratios to tailor the emittance. Nonetheless, this study represents the first generation and reported emittance data of UHTC doping ZBS systems with both Sm and Er elements.

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46

Wu, Wun-Hao, and 吳文皓. "The effect of rare earth element doping on the characteristics of LiFePO4 for Lithium-ion Batteries." Thesis, 2012. http://ndltd.ncl.edu.tw/handle/74568834725211127373.

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碩士
國立雲林科技大學
化學工程與材料工程系碩士班
100
In this study, iron ore was used as Fe-precursor to produce iron phosphate by co-precipitation. By utilizing the product and lithium carbonate as a precursor, and ascorbic acid as a carbon source, LiFePO4 and LiNdxFe1-xPO4(x=0.3、0.5、1、2 mole% ) can be produced by solid method as cathode materials for secondary lithium ion batteries. In order to investigate the effect of charge-discharge property, lattice structure, conductivity, particel size, surface morphology of Nd-doped and undoped FePO4 and Nd-doped and undoped LiFePO4/C were study. In addition, the P/Fe molar ratio of iron phosphate was determined. The prepared sample were characterized by X-ray Diffraction(XRD), Ultraviolet/Visible (UV/vis), Thermogravimetric Analysis(TGA), Atomic Absorption Spectrometer(AAS), Dynamic Light Scattering(DLS), Filed Emission Scanning Electron Microscope (FE-SEM), Transmission Electron Microscope (TEM), Energy Dispersive Spectrometer(EDS), conductivity measurement, galvanostatic charge-discharge analyses. According to XRD result, the change in lattice parameter from Nd doping, indicating the peak shifted for FePO4 and LiFePO4/C is from 0.04° to 0.08° and 0.02° to 0.06°, respectively. The 0.3 mol.% Nd-doped FePO4 and the LiFePO4 exhibits small average particle size of 62 nm and 104 nm, respectively. In addition, SEM images show that agglomeration occurs in both FePO4 and LiFePO4/C when the doping content exceeds 0.5 mol.% Nd, which affects the charge-discharge capacity. The results, suggest that crystal growth of FePO4 in uniform solution leads to agglomeration and thus larger particle size. The charge-discharge test results show that the 0.3 mole% Nd-doped LiFePO4/C remains at the initial capacity of 91.5%、90.5% and 90.5% at rates of 0.5C、1C and 3C respectively, after 50 cycle. The undoped LiFePO4/C were remains at initial capacity of 70.3%、77.6% and 87.7% at rates of 0.5C、1C and 3C, respectively, after 50 cycle. As a result, the Nd-doped LiFePO4/C shows a better cycle capability than that of the undoped LiFePO4/C.

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47

Ferguson, Katherine Rose. "Generation and storage of optical entanglement in a solid state spin-wave quantum memory." Phd thesis, 2016. http://hdl.handle.net/1885/109193.

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This thesis investigates an entangled light source with an in-built quantum memory based on the protocol of rephased amplified spontaneous emission (RASE). RASE has promising applications as a building-block of a quantum repeater: a device essential for extending the range of current quantum communication links. To be useful RASE must be able to produce high fidelity non-classical light with high efficiency, and be able to store multimode entanglement for long times. This thesis characterises the RASE source and determines to what degree these requirements can be met. The experimental RASE demonstration was conducted in a rare-earth ion doped crystal. Rare-earth ions provide a particularly promising platform for developing quantum technologies as they possess long coherence times on both the optical and hyperfine transitions. In the RASE protocol an inverted ensemble of two-level atoms amplifies the vacuum fluctuations resulting in amplified spontaneous emission (ASE). This results in entanglement between the output optical field and the collective modes of the amplifying ensemble. The collective atomic state dephases due to the inhomogeneous broadening of the ensemble but this can be rephased using photon echo techniques. When the ensemble rephases, a second optical field, the rephased amplified spontaneous emission (RASE), is emitted and is entangled with the ASE. In this thesis, a modified four-level rephasing scheme is used that allows the single photon signals to be spectrally resolved from any coherent background emission associated with the bright driving fields. In addition, four-level RASE incorporates storage on the long-lived hyperfine ground states. Two experiments are described in this thesis. First, a free-space four-level RASE demonstration using continuous-variable detection. In this experiment the different sources of noise were characterised and low noise operation was shown to be possible. Entanglement of the ASE and RASE was confirmed by violating the inseparability criterion with 98.6% confidence. In addition, entanglement was demonstrated after storage of the collective atomic state on the spin states and RASE was shown to be temporally multimode, with almost perfect distinguishability between two temporal modes demonstrated. The degree of entanglement between the ASE and RASE was limited by the rephasing efficiency, which saturated at 3%. It was determined that distortion of the rephasing pulses as they propagate through the optically thick ensemble was the probable cause of the low efficiency. The second experiment was a preliminary cavity-enhanced RASE demonstration. Theoretically perfect rephasing efficiency can be obtained by placing the crystal in an impedance-matched optical cavity. The initial cavity design showed encouraging evidence of an enhancement in the rephasing efficiency, with a 4-fold improvement over the free-space experiment. Improvements to the cavity design were proposed to allow a further increase in the rephasing efficiency of RASE. In summary, this thesis provides an extensive characterisation of an entangled light source with an in-built quantum memory based on rephasing spontaneous emission from an ensemble of ions. Importantly, the RASE scheme allows generation and storage of entanglement in a single protocol, which holds great promise for the development of integrated quantum networks.

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48

Honnavar, Gajanan V. "Mixed Alkali Effect in Oxyfluoro Vanadate Glasses And The Effect of Rare Earth Ions on Oxyfluoro Tellurite Glasses - A Spectroscopic Study." Thesis, 2016. http://etd.iisc.ernet.in/handle/2005/2667.

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The main motivation of this thesis is to study the long standing problem of mixed alkali effect (MAE) in oxyfluro vanadate glass systems from the point of view of structural arrangement and to investigate the effect of two rare earth ions, namely, erbium and europium on the structure of tellurium dioxide based glass. In glass science, it is well known that when one alkali in a glass matrix is gradually replaced by another alkali, leads to a non-linear variation in some of the physical properties. There are many a theories trying to explain this effect. Recently the renewed interest lies in explaining MAE in-terms of structural consideration. Rare earth (RE) ion doped glasses are of interest in a variety of applications in photonics because of the special optical properties exhibited by these materials. Atomic like f-f transitions of RE ions depend on the local environment of the these ions. A particular glass matrix may be able to bring out the optical properties of a RE ion better than the other matrix. In this regard structural characterization of a glass matrix with different RE ions for optical properties is of importance. Spectroscopic tech-niques are best suited to investigate structural arrangement in glasses and in this thesis we have used techniques like Raman, electron paramagnetic resonance (EPR), impedance, photoluminescence and UV- visible absorption spectroscopies. The thesis comprises of five chapters and an appendix. Chapter 1 consists of brief introduction of general properties of glasses and their behavior under different spectroscopic techniques. Chapter 2 deals with the sample preparation and the experimental techniques used in this work. Chapter 3 elaborates on the Raman and EPR spectroscopic studies on the structural arrangement of the mixed alkali oxyfluro vanadate glass systems. Chapter 4 focuses on the ac and electrical modulus analysis to study the MAE in the above samples. Chapter 5 deals with the optical spectroscopic techniques used to study the compatibility of RE ions (erbium and europium) with the tellurium dioxide based glass matrix. Chapter 1: Disordered materials pose a challenge to understand their structure mainly because of their random arrangement of the constituent units. In this chapter the glassy systems and the different experimental techniques used to study them are discussed in general. The behavior of glassy systems to the external stimuli in various frequency ranges is highlighted. A short review of mixed alkali effect in glasses mainly covering the advances in the last two decades is given. Brief outline of the theory of Raman, EPR and ac impedance spectroscopy are given. Chapter 2: This chapter discusses the major experimental techniques used in the thesis to study the glass systems at block diagram level. The Raman and EPR spectrometers are discussed. Experimental technique used in ac impedance measurement is outlined. Different methods of preparing glass are listed and melt quenching technique is discussed in detail. Chapter 3: This chapter discusses the results and analysis of Raman and EPR study in oxyfluoro vanadate glasses emphasizing MAE. The glass having batch formula 40V2O5 - 30BaF2 - (30 - x) LiF - xRbF (x = 0 – 30) is prepared by melt quenching technique. Raman spectroscopic study in back scattering geometry is performed to see the effect of alkali ions on the V – O bond length of VO6 polyhedra in the glass. The de-convoluted Raman peaks corresponding to V = O and VO2 are considered and the effect of alkali mixture on these bonds are studied. • The peak shift of V = O and VO2 bonds shows that V = O is affected only a little by the replacement of lithium (Li) by rubidium (Rb), while VO2 bond gets affected to a larger extent. • From the peak shift the most probable value of the bond length and the spread in it are estimated. The bond length corresponding to V = O is found to increase and that of VO2 decrease as a consequence of alkali replacement. • From the FWHM of the corresponding Raman peaks, it is concluded that O - Rb coordination sphere around VO6 polyhedra is more homogeneous than either O – Li or O - Li /Rb coordination. These results are published in J. Non-Cryst. Solids 370 (2013) 6. EPR studies on the samples are carried out in X band frequency and spin – Hamilto-nian parameters were extracted by simulating and fitting the EPR spectra to experimental data using EasySpin which is a Matlab toolbox. • it is observed that the ratio 4gjj=4g?, which is a measure of tetragonality of octa-hedral crystal symmetry of V2O5, varies non-monotonically with Rb content. • A model based on this observation is proposed. The essential idea of this model is that Rb atoms that are substituted for Li atoms initially prefer terminal positions over planar positions. Continued substitution then replaces planar Li atoms. It is seen that this model of “preferential substitution” explains the observation very well. • Another observation is that the EPR signal intensity, which is due to concentration of V4+ ions, also shows non-monotonous behavior with Rb content. This is also explained using preferential substitution, taking into consideration the oxidation states of the vanadium ions. • The value of 4gjj=4g?, is a minimum for all rubidium environments around V2O5, which infers that Rb coordination is more symmetric than all Li or Li−Rb. • A good correlation is found between Raman and EPR study of the above system. These results are published in J. Phys. Chem. A 118 (2014) 573. Chapter 4: The chapter brings out the results of ac conductivity and electrical mod-ulus study of MAE in the glass system mentioned above. The Agilent 4294A precision impedance analyzer operating in frequency range 40 Hz to 110 MHz, is used for per-forming impedance and capacitance experiments carried out in this thesis. Impedance measurements in our studies are performed in sandwich geometry. • Room temperature dc conductivity shows a decrease as Li is replaced by Rb and reaches its minimum - five orders less than its all Li value at 0.33 molar fraction of Rb, which is attributed to MAE. This observation is explained using the structural aspect. • Using the linear response theory the number of mobile ions participating in the conduction is estimated. • Imaginary part of the electrical modulus is fitted to Kohlrausch – Williams – Watts (KWW) relation by using a complex nonlinear least squares fitting procedure given by Bergmann. • The stretching parameter b estimated from the above procedure is found to exhibit MAE. The observed variation in b with Rb mole fraction is explained by taking into considerations the contributions from fast and slow processes, and coupling between different relaxing sites. The manuscript is under preparation. Chapter 5: This chapter illustrates the optical study of RE doped TeO2 based glasses to determine the suitability of a particular RE ion with a given glass matrix. TeO2 based glasses having a general formula (in mol %) 65TeO2 – 5BaF2 – 30ZnF2 (TBZ) were prepared by usual melt quenching technique. RE doping was done at the expense of TeO2. 3 mol % of Eu or Er are added to prepare RE doped glass. Raman, PL, UV-visible absorption studies are carried out on the glass samples. • From the peak shift, intensity variation and FWHM of the Raman spectra of the glass samples it is observed that Eu doped TBZ glass has a greater tendency towards depolymerizing the glass matrix by influencing the conversion of TeO4 units into the formation of TeO3 units. • PL spectra of the glass samples shows emission due to different possible transitions. Position of the peak of the de-convoluted spectra shows the position of the particular Stark component and the FWHM is a measure of the inhomogeneous broadening. • The UV-visible absorption spectra are used to calculate the optical density and fitted to the Mott equation to determine the band edge of the glass samples. It is seen that Eu doped TBZ glass has a lesser band gap than that of Er doped glass. The manuscript is submitted to Bul. Mat. Sci. Appendix : This consists of a collection of details of EDS study carried on the VBL series glasses and some MATLAB codes used to simulate the EPR spectrum for VBL series glasses.

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