Literatura académica sobre el tema "Glass doping"

The nonlinear optical properties of a semiconductor-doped glass (SDG) channel waveguide were measured on a picosecond time-scale; namely, fluence-dependent changes in the absorption and the refractive index as well as the relaxation time of the nonlinearity. Slower, thermally-induced changes in the refractive index were also observed. The saturation of the changes in the absorption and the refractive index with increasing optical fluence is explained using a plasma model with bandfilling as the dominant mechanism. The fast relaxation time of the excited electron-hole plasma (20 ps) is explained using a surface-state recombination model. A figure of merit for a nonlinear directional coupler fabricated in a material with a saturable nonlinear refractive index is presented. The measured nonlinear change in the refractive index of the SDG saturates below the value required to effect fluence-dependent switching in a nonlinear directional coupler. Experiments with a channel-waveguide directional coupler support this prediction. However, absorption switching due to differential saturation of the absorption in the two arms of the directional coupler was observed.

In this thesis study, fabrication and doping of silicon thin films prepared by electron beam evaporation equipped with effusion cells for solar cell applications have been investigated. Thin film amorphous Si (a-Si) layers have been fabricated by the electron beam evaporator and simultaneously doped with boron (B) and phosphorous (P) using effusion cells. Samples were prepared on glass substrates for the future solar cell operations. Following the deposition of a-Si thin film, crystallization of the films has been carried out. Solid Phase Crystallization (SPC) and Metal Induced Crystallization (MIC) have been employed to obtain thin film crystalline Si. Crystallization was performed in a conventional tube furnaces and Rapid Thermal annealing systems (RTA) as a function of process parameters such as annealing temperature and duration. Produced films have been characterized using chemical and structural characterization techniques such as Raman Spectroscopy, X-Ray Diffractometer and Secondary Ion Mass Spectrometer (SIMS). The electrical properties of the films have been studied using Hall Effect and I-V measurements as a function of doping. We have demonstrated successful crystallization of a-Si by SPC at temperatures above 600 &deg<br>C. The crystallization occurred at lower temperatures in the case of MIC. For doping, P was evaporated from the effusion cell at a temperature between 600 &deg<br>C and 800 &deg<br>C. For B, the evaporation temperature was 1700 &deg<br>C and 1900 &deg<br>C. The thickness and the band gap of the Si films were determined by ellipsometry method and the results were compared for different evaporation temperatures. The effect of doping was monitored by the I-V and Hall Effect measurements. We have seen that the doping was accomplished in most of the cases. For the samples annealed at relatively high temperatures, the measured doping type was inconsistent with the expected results. This was attributed to the contamination from the glass substrate. To understand the origin of this contamination, we analyzed the chemical structure of the film and glass by X-ray Fluorescence (XRF) and seen that the glass is the main source of contamination. In order to prevent this contamination we have suggested covering the glass substrate with Si3N4 (Silicon Nitride) which act as a good diffusion barrier for impurities.

Made available in DSpace on 2014-06-11T19:25:33Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-06-28Bitstream added on 2014-06-13T18:28:59Z : No. of bitstreams: 1 gordo_vo_me_ilha.pdf: 1058796 bytes, checksum: 2c8438704796726349dfe606c2595b4b (MD5)<br>Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)<br>Neste trabalho foi estudado o sistema vítreo (100-x)% (80% TeO2-20% WO3)-(x)% Yb2O3, onde x = 0; 0,1; 0,2; 0,3; 0,4 e 0,5%. As técnicas de difração de raios-X, espectroscopia no infravermelho, espectroscopia Raman e espectroscopia no UV-Vis foram usadas para caracterizar os efeitos da dopagem sobre as propriedades estruturais e ópticas dos vidros estudados. Usando os dados de espectroscopia na região espectral ultravioleta-visível foi possível observar que não houve mudança das freqüências de corte para cada composição e ainda calcular a energia de “gap” e a energia de cauda de Urbach. Usando os dados de fotoluminescência observam-se picos que indicam o desdobramento dos níveis de energia dos estados 2F7/2 e 2F5/2 dos íons de Yb3+. Para os comprimentos de onda de excitação de 514,5 a 488,0 nm, crescem as taxas de absorção do sistema vítreo TW, transferência de carga para o estado 2F5/2 do Yb3+ e da transição radiativa 2F5/2 2F7/2, aumentando, desta forma, a intensidade da fotoluminescência. Já para os comprimentos de onda de excitação 457,9 e 476,5 nm as taxas de absorção do sistema vítreo TW, a transferência de carga para o estado 2F5/2 do Yb3+ e a transição radiativa 2F5/2 2F7/2 são as mesmas e, consequentemente, a intensidade da fotoluminescência é constante.<br>This work presents the study on the glassy system (100-x)% (80% 20% TeO2-WO3) - (x)% Yb2O3 where x = 0, 0.1, 0.2, 0.3, 0.4 and 0 5%. The techniques of X-ray diffraction, infrared spectroscopy, Raman spectroscopy and UV-Vis were used to characterize the effects of Yb doping on the structural and optical properties of the glasses. Using data from spectroscopy ultraviolet-visible spectral region was observed that there was no change of cutting frequencies for each compound and were calculate the energy gap and Urbach tail energy. Using the data of photoluminescence peak is observed indicating the splitting of energy levels of states 2F7/2 and 2F5/2 of Yb3+ ions. The rate of electron transition probability is influenced by temperature. To the excitation wavelength of 514.5 to 488.0 nm, growing rates of absorption of the glass system TW, charge transfer to the state 2F5/2 of Yb3+ and the radiative transition 2F5/2 2F7/2, increasing thus the photoluminescence intensity. As for the excitation wavelength of 476.5 and 457.9 nm absorption rates of the TW glass system, the charge transfer state to the 2F5/2 of Yb3+ and the radiative transition 2F5/2 2F7/2 are the same and, hence the photoluminescence intensity is constant.

Chalcogenide glasses and glass-ceramics present a high interest for the production of thermal imaging lenses transparent in the 3-5 μm and 8-12 μm windows. However, chalcogenide glasses are conventionally synthesized in sealed silica ampoules which have two major drawbacks. First, the low thermal conductivity of silica limits the sample dimensions and second the silica tubes employed are single use and expensive, and represent up to 30% of the final cost of the material. The present work therefore addresses the development of innovative synthesis methods for chalcogenide glass and glass-ceramics that can present an alternative to the silica tube route. The method investigated involves melting the raw starting elements in reusable silica containers. This method is suitable for the synthesis of stable chalcogenide glasses compositions such as GeSe₄ but uncontrolled crystallization and homogenization problems are experienced for less stable compositions. The second approach involves preparation of amorphous chalcogenide powders by ball milling of raw elements. This mechanosynthesis step is followed by consolidation of the resulting powders to produce bulk glasses. Hot Uniaxial Pressing is suitable for compositions stable against crystallization. However, uncontrolled crystallization occurs for the unstable 80GeSe₂-20Ga₂Se₃ glass composition. In contrast consolidation through Spark Plasma Sintering (SPS) allows production of bulk glasses in a short duration at relatively low temperatures and is appropriate for the synthesis of unstable glasses. A sintering stage of only 2 min at 390°C is shown to be sufficient to obtain infrared transparent 80GeSe₂-20Ga₂Se₃ bulk glasses. This method enables the production of lenses with a 4-fold increase in diameter in comparison to those obtained by melt/quenching technique. Moreover, increasing the SPS treatment duration yielded infrared transparent glass-ceramics with enhanced mechanical properties. This innovative synthesis method combining mechanosynthesis and SPS has been patented in the framework if this study. The controlled etching of 80GeSe₂-20Ga₂Se₃ glass-ceramics in acid solution yields nanoporous materials with enhanced surface area. The porous layer created on the surface of the glass-ceramic is shown to play the role of anti-reflection coating and increase the optical transmission in the infrared range by up to 10%. These materials may have potential for the production of sensors with increased sensitivity in the infrared. The influence of indium and lead addition on the thermal and optical properties of the 80GeSe₂-20Ga₂Se₃ glass has also been assessed. Increased In or Pb contents tend to decrease the Tg of the glasses and shift the optical band gap toward higher wavelengths. A systematic ceramization study emphasizes the difficulty of controlling the crystallization for glasses in the systems GeSe₂-Ga₂Se₃-In₂Se₃ and GeSe₂-Ga₂Se₃-PbSe. No crystallization of the In₂Se₃ and PbSe crystalline phase was obtained. Finally, the possibility of producing rare-earth doped 80GeSe₂-20Ga₂Se₃ glass-ceramics transparent in the infrared region up to 16 μm is demonstrated. Enhanced photoluminescence intensity and reduced radiative lifetimes are observed with increased crystallinity in these materials.

Les verres de phosphates à faible Tg et forte stabilité thermique sont étudié dans le système (66-x)ZnO- xNa2O-33.4 P2O5. Les mesures DSC ont montré un écart Tx-Tg de 197 °C et une Tg de 339 °C pour x= 20. La RMN 31P 1D/2D révèle la diminution du désordre due à la substitution progressive de Zn par Na. Les formulations x=20 et x=33 ont été dopé par de l’Al2O3, B2O3 et SiO2 (1-4 % mol.) et ses effets sur les propriétés physiques comme la température de transition vitreuse, la stabilité thermique et la durabilité chimique ont été investiguées. La DRX et la RMN 31P ont été réalisés pour suivre le processus de cristallisation en isotherme à 130°C (au-delà de la Tg). La plus forte stabilité thermique a été identifiée pour les verres dopés au bore. Le Raman et la RMN 31P ont mis en évidence l’existence de connections P-O-X (X=27Al ou 11B). La RMN a entre autre montré la coordinence majoritaire VI, IV et IV respectivement pour l’aluminium, le bore et la silice. L’utilisation de D-INEPT, REDOR et DQ-SQ permet d’approfondir nos connaissances sur la structure particulièrement sur les connectivités P-O-X mais également la diversité des connections possibles<br>Pyrophosphate glass with low Tg and high stability is investigated within the (66-x) ZnO- xNa2O-33.4 P2O5 system. DSC measurement indicated Tx-Tg=197 °C with Tg = 339 °C at x= 20. 1D/2D 31P NMR revealed the decrease in extent of disorder with the progressive substitution of Zn by Na. The x=20 and x=33 formulations were doped with (1-4 mol.%) of Al2O3, B2O3 and SiO2 and its effect on the physical properties such as the glass transition temperature, thermal stability and chemical durability is investigated. XRD and 1D 31P solid state NMR were used to monitor the isothermal crystallization process occurring at 130 °C above Tg and the highest thermal stability is presented by the B-doped glasses. Raman and 31P NMR suggested the existence of P-O-X (X=27Al or 11B) bonds. The MAS NMR distinguished the dominant coordination states of doping elements AlVI , BIV and SiIV respectively. The use of D-INEPT, REDOR and DQ-SQ helped in producing deeper insights onto the glass structure about the P-O-X connectivity, the wide range of phosphate speciation

Orientador: Keizo Yukimitu<br>Banca: José Brás Barreto Oliveira<br>Banca: Noelio Oliveira Dantas<br>Resumo: Neste trabalho foi estudado o sistema vítreo (100-x)% (80% TeO2-20% WO3)-(x)% Yb2O3, onde x = 0; 0,1; 0,2; 0,3; 0,4 e 0,5%. As técnicas de difração de raios-X, espectroscopia no infravermelho, espectroscopia Raman e espectroscopia no UV-Vis foram usadas para caracterizar os efeitos da dopagem sobre as propriedades estruturais e ópticas dos vidros estudados. Usando os dados de espectroscopia na região espectral ultravioleta-visível foi possível observar que não houve mudança das freqüências de corte para cada composição e ainda calcular a energia de "gap" e a energia de cauda de Urbach. Usando os dados de fotoluminescência observam-se picos que indicam o desdobramento dos níveis de energia dos estados 2F7/2 e 2F5/2 dos íons de Yb3+. Para os comprimentos de onda de excitação de 514,5 a 488,0 nm, crescem as taxas de absorção do sistema vítreo TW, transferência de carga para o estado 2F5/2 do Yb3+ e da transição radiativa 2F5/2 2F7/2, aumentando, desta forma, a intensidade da fotoluminescência. Já para os comprimentos de onda de excitação 457,9 e 476,5 nm as taxas de absorção do sistema vítreo TW, a transferência de carga para o estado 2F5/2 do Yb3+ e a transição radiativa 2F5/2 2F7/2 são as mesmas e, consequentemente, a intensidade da fotoluminescência é constante.<br>Abstract: This work presents the study on the glassy system (100-x)% (80% 20% TeO2-WO3) - (x)% Yb2O3 where x = 0, 0.1, 0.2, 0.3, 0.4 and 0 5%. The techniques of X-ray diffraction, infrared spectroscopy, Raman spectroscopy and UV-Vis were used to characterize the effects of Yb doping on the structural and optical properties of the glasses. Using data from spectroscopy ultraviolet-visible spectral region was observed that there was no change of cutting frequencies for each compound and were calculate the energy gap and Urbach tail energy. Using the data of photoluminescence peak is observed indicating the splitting of energy levels of states 2F7/2 and 2F5/2 of Yb3+ ions. The rate of electron transition probability is influenced by temperature. To the excitation wavelength of 514.5 to 488.0 nm, growing rates of absorption of the glass system TW, charge transfer to the state 2F5/2 of Yb3+ and the radiative transition 2F5/2 2F7/2, increasing thus the photoluminescence intensity. As for the excitation wavelength of 476.5 and 457.9 nm absorption rates of the TW glass system, the charge transfer state to the 2F5/2 of Yb3+ and the radiative transition 2F5/2 2F7/2 are the same and, hence the photoluminescence intensity is constant.<br>Mestre

La modulation de la densité de charge est un aspect important de l'étude de les transitions de phase électroniques ainsi que des propriétés électroniques des matériaux et il est à la base de plusieurs applications dans la micro-électronique. L'ajustement de la densité des porteurs de charge (dopage) peut être fait par voie chimique, en ajoutant des atomes étrangers au réseau cristallin du matériau ou électrostatiquement, en créant un accumulation de charge comme dans un Transistor é Effet de Champ. Cette dernier m ethode est réversible et particuliérement appropriée pour les matériaux bidimensionnels (2D) ou pour des couches ultra-minces. Le Dopage par Charge d'Espace est une nouvelle technique inventée et développée au cours de ce travail de thèse pour le dopage electrostatique de matériaux déposés sur la surface du verre. Une charge d'espace est créée à la surface en provoquant le mouvement des ions sodium présents dans le verre sous l'effet de la chaleur et d'un champ électrique extérieur. Cette espace de charge induit une accumulation de charge dans le matériau déposé sur la surface du verre, ce qui peut être supérieure à 10^14/cm^2. Une caractérisation détaillée faite avec mesures de transport, effet Hall, mesures Raman et mesures de Microscopie a Force Atomique (AFM) montrent que le dopage est réversible, bipolaire et il ne provoque pas des modifications chimiques. Cette technique peut être appliquée a des grandes surfaces, comme il est montré pour le cas du graph ene CVD. Dans une deuxiéme partie le dopage par espace de charge est appliqué à des couches ultra-minces (&lt; 40 nm) de ZnO_(1-x). Le résultat est un abaissement de la résistance par carré de 5 ordres de grandeur. Les mesures de magnéto-transport faites à basse température montrent que les électrons dop es sont confinés en deux dimensions. Une transition remarquable de la localisation faible à l'anti-localisation est observée en fonction du dopage et de la température et des conclusions sont tirées à propos des phénoménes de diffusion qui gouverne le transport électronique dans des diff erentes conditions dans ce matériau<br>Carrier modulation is an important parameter in the study of the electronic phase transitions and the electronic properties of materials and at the basis for many applications in microelectronics. The tuning of charge carrier density (doping) can be achieved chemically, by adding foreign atoms to the crystal structure of the material or electrostatically, by inducing a charge accumulation like in a Field Eect Transistor device. The latter method is reversible and particularly indicated for use in two dimensional (2D) materials or ultra-thin films. Space Charge Doping is a new technique invented and developed during this thesis for the electrostatic doping of such materials deposited on a glass surface. A space charge is created at the surface by causing sodium ions contained in glass to drift under the Eect of heat and an external electric field. This space charge in turn induces a charge accumulation in the material deposited on the glass surface which can be higher than 10^14/cm^2. Detailed characterization using transport, Hall effect, Raman and AFM measurements shows that the doping is reversible, ambipolar and does not induce chemical changes. It can be applied to large areas as shown with CVD graphene. In a second phase the space charge doping method is applied to polycrystalline ultra-thin films (&lt; 40 nm) of ZnO_(1-x). A lowering of sheet resistance over 5 orders of magnitude is obtained. Low temperature magneto-transport measurements reveal that doped electrons are confined in two dimensions. A remarkable transition between weak localization and anti-localization isobserved as a function of doping and temperature and conclusions are drawn concerning the scattering phenomena governing electronic transport under different conditions in this material

L’accroissement de l’espérance de vie s’accompagne d’une détérioration de l’état de santé général des seniors et d’une recrudescence des maladies chroniques. Parmi les manifestations de la sénescence, l’atteinte de l’appareil locomoteur est particulièrement invalidante et accélère considérablement l’entrée en dépendance. C’est également le cas chez les plus jeunes lors d’atteintes traumatiques ou pathologiques. Ainsi, au niveau mondial 2,2 millions de greffes osseuses sont pratiquées chaque année, mais le taux de complications post-opératoires demeure élevé et est estimé à 15 % des interventions. Ces faits dessinent les contours d’un enjeu sociétal majeur ; les matériaux d’origine animale posent des problèmes d’histocompatibilité, de pathogénicité et donc de rejet. C’est pourquoi les efforts de recherche ciblent prioritairement le développement de biomatériaux synthétiques aptes à promouvoir la régénération osseuse. Actuellement les principaux substituts osseux sur le marché sont les « céramiques » bioactives (phosphates de calcium, verres bioactifs) qui présentent comme caractéristiques d’être biocompatibles, de se lier spontanément aux tissus osseux, de promouvoir l’adhésion des cellules osseuses et enfin d’être biorésorbables. Cependant, malgré cet ensemble de caractéristiques très satisfaisantes, la fragilité de ces matériaux en limite les applications. Pour pallier ce défaut, une solution ingénieuse est de s’inspirer de la structure particulière du tissu osseux. Celle-ci mêle intimement une phase inorganique, le minéral osseux constitué de cristaux d’apatite (phosphate de calcium résorbable), à une phase organique qui est majoritairement du collagène. De manière remarquable, une telle structure associe la rigidité de la partie inorganique à la ténacité des fibres de collagène. Pour obtenir des implants aux propriétés mécaniques proches du tissu osseux, la stratégie consiste donc à combiner céramiques bioactives et matière organique. À cette fin, l’équipe Biomatériaux du Laboratoire de Physique de Clermont (LPC) a récemment mis au point un procédé innovant qui permet la synthèse de matrices tridimensionnelles d’hybrides organique-inorganique à base de verre bioactif et de polymère biocompatible aux caractéristiques variées. Dans la continuité des travaux, il était alors question d’exploiter ce procédé afin de développer un substitut osseux hybride aux propriétés optimisées. Il s’agissait tout d’abord de sélectionner le polymère le plus adéquat pour la régénération osseuse, qui s’est avéré être le polycaprolactone, puis d’optimiser la synthèse (notamment la source de calcium), la structure macroporeuse et la proportion organique-inorganique. Le matériau hybride résultant a ensuite été dopé en éléments thérapeutiques à faible dose (&lt; 5 % de la masse totale) avec des ions strontium ou des nutriments tels que la fisétine et l’hydroxytyrosol qui possèdent un effet ostéogénique. Les mousses hybrides ainsi développées ont finalement été caractérisées in vitro afin de déterminer leurs propriétés physico-chimiques et biologiques, et in vivo afin d’évaluer leur performance. Après 3 mois d’implantation dans un défaut critique de la calvaria de souris, les résultats démontrent le potentiel de ce substitut osseux: comparé au matériau commercial de référence (os bovin traité) qui conduit à une reconstruction osseuse de 16% (± 5%), l’hybride permet une reconstruction allant de 32% (± 3%) lorsqu’il n’est pas dopé, jusqu’à 55% (± 7%) voire 58% (± 7%) lorsqu’il est dopé respectivement en fisétine ou en strontium. Ces travaux de thèse laissent entrevoir des perspectives prometteuses telles que l’association des dopants et l’impression 3D des mousses hybrides polycaprolactone-verre bioactif<br>The increase in life expectancy results in the decline of seniors’ health conditions and the resurgence of chronic diseases. Among the expressions of senescence, disorders of the musculoskeletal system are particularly disabling and considerably accelerate the state of dependency. This is also the case for young people who suffer from traumatic injuries or pathologic conditions. Thus, about 2.2 million bone grafts are performed worldwide every year. Yet, the level of postoperative complications remains high and is estimated at 15% of surgical operations. These facts outline a major societal concern: animal-based materials present a risk of histocompatibility issues and pathogenicity that may lead to implant failure. This is the reason why research efforts focus on the development of synthetic biomaterials capable of promoting bone regeneration. Currently, commercialised bone substitutes are mainly made of bioactive “ceramics” (calcium phosphates, bioactive glass) that are known to be biocompatible, to spontaneously bond to bone tissues, to promote bone cell adhesion and finally to be bioresorbable. However, despite these remarkable properties, the brittleness of these materials limits their applications. An ingenious solution to this brittleness can be learned from the particular structure of bone tissue. Bone tissue intimately blends an inorganic phase, the bone mineral, which is made of apatite crystals (resorbable calcium phosphates), with an organic phase that is mainly collagen. Such a structure associates the stiffness of the inorganic part with the toughness of collagen fibres. Therefore, in order to obtain implants with mechanical properties similar to that of bone, the strategy consists in combining bioactive ceramics with organic matter. To this end, the Biomatériaux team from the Laboratoire de Physique de Clermont (LPC) recently developed an innovative process that allows the synthesis of tridimensional organic-inorganic hybrids comprised of bioactive glass and biocompatible polymer. The objective of the thesis was to exploit this process in order to develop a hybrid bone substitute with optimal properties. First of all, polycaprolactone was selected as the polymer, especially because of its adequate degradation rate for long-term applications such as bone regeneration. Then, the synthesis process was improved (in particular, the calcium source was changed), the macroporous structure was optimised and the organic-inorganic ratio was chosen. Afterwards, elements that are known to induce an osteogenic effect were incorporated in the hybrid at low doses (&lt; 5% of total weight): an inorganic doping was performed using strontium ions and an organic doping was performed using nutrients such as fisetin or hydroxytyrosol. The resultant hybrid scaffolds were eventually characterised in vitro in order to determine their physicochemical and biological properties and in vivo in order to evaluate their performance. After 3 months of implantation in a mouse calvarial critical defect, results demonstrate the potential of this bone substitute: compared to the reference commercial material (treated bovine bone) that leads to a bone reconstruction of 16% (± 5%), the hybrid allows a reconstruction going from 32% (± 3%) when it is not doped, to 55% (± 7%) and even 58% (± 7%) when it is doped respectively with fisetin or strontium. This thesis paves the way to promising perspectives like the association of doping agents and the 3D printing of polycaprolactone-bioactive glass hybrid scaffolds