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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
691

Uma Analise no dominio espectral do mecanismo de travamento de modos

WETTER, NIKLAUS U. 09 October 2014 (has links)
Made available in DSpace on 2014-10-09T12:38:06Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:05:53Z (GMT). No. of bitstreams: 1 05639.pdf: 6476184 bytes, checksum: 3037d7c0ce96c51e46c15baa5bdd114c (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP / FAPESP:92/01672-4
692

Caracterização óptica de filmes finos de NbOx obtidos por sputtering reativo / Optical characterization of NbOx thin films obtained by reactive sputtering

SCHEIDT, GUILHERME 20 February 2015 (has links)
Submitted by Maria Eneide de Souza Araujo (mearaujo@ipen.br) on 2015-02-20T13:22:28Z No. of bitstreams: 0 / Made available in DSpace on 2015-02-20T13:22:28Z (GMT). No. of bitstreams: 0 / Filmes finos de óxido de nióbio têm sido usados em muitas aplicações tecnológicas. Existem pelo menos três óxidos estáveis de nióbio: NbO, NbO2 e Nb2O5 e cada um deles tem propriedades específicas. O Nb2O5 é a forma termodinamicamente mais estável e apresenta propriedades físicas e químicas únicas, como alto índice de refração, band gap largo, excelente estabilidade química e resistência à corrosão, baixa absorção óptica no campo da luz visível até regiões próximas ao infra-vermelho, sendo amplamente utilizados como filtros de interferência óptica de alta qualidade. Neste trabalho foram depositados filmes de óxido de nióbio por meio da técnica de sputtering reativo sobre substratos de silício e borossilicato. Os filmes finos foram obtidos com vazão de oxigênio variando entre 15 e zero sccm. O objetivo deste trabalho foi a caracterização das propriedades ópticas dos filmes. Foram avaliados o índice de refração e a espessura pela técnica de elipsometria, o band gap pelo método de Tauc e a razão atômica e a densidade superficial por meio de Espectrometria de Retroespalhamento Rutherford (RBS). Foram obtidos espectros de transmitância e refletância por Espectrofotometria UV/Vis/NIR e o coeficiente de extinção foi calculado pelo método de Hong. Todos estes parâmetros são importantes para aplicação em dispositivos ópticos. Nos filmes depositados com vazão de oxigênio de 15 sccm foi observado que o índice de refração aumenta com o aumento da espessura dos filmes e que o composto formado foi Nb2O5. Para uma vazão de 2,0 sccm foi encontrado o composto NbO2 e o filme apresentou alta absorção ótica. Os resultados sugerem que outros óxidos de nióbio ou nióbio metálico foram incorporados nos filmes conforme o fluxo de oxigênio foi diminuído. Foi observada uma relação direta entre a diminuição da vazão de oxigênio durante a deposição e um aumento da quantidade de nióbio nos filmes, acompanhados de um aumento do índice de refração e da densidade superficial. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP
693

Propriedades opticas e eletricas de nanoestruturas de Si / Optical and electrical properties of silicon nanostructures

Dias, Guilherme Osvaldo 12 August 2018 (has links)
Orientador: Jacobus Willibrordus Swart / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Eletrica e de Computação / Made available in DSpace on 2018-08-12T22:45:26Z (GMT). No. of bitstreams: 1 Dias_GuilhermeOsvaldo_D.pdf: 3822925 bytes, checksum: 25e0dd51fed5d5d3cb7dc334a0a61bb7 (MD5) Previous issue date: 2009 / Resumo: Analisamos amostras de óxido de silício rico em silício (SRSO) obtidas por um sistema de deposição química de vapor com ressonância ciclotrônica de elétrons (ECR-CVD). Propriedades estruturais, de composição, ópticas e elétricas foram estudadas por transformada de Fourier de absorção no infravermelho (FTIR), microscopia eletrônica de transmissão (TEM), espectroscopia de retro-espalhamento Rutherford (RBS), fotoluminescência (PL), elipsometria e medidas de capacitância-tensão (C-V). Através do ajuste dos índices de refração em função do fluxo de O2 para uma longa faixa de razões de fluxo, pudemos notar que o sistema ECR-CVD permite obter filmes com alto controle desses índices de refração. Isto sugere indiretamente a possibilidade do controle das características ópticas e elétricas dos nossos filmes, pois essas características, assim como o índice de refração, são dependentes da concentração de silício nos filmes. Na região de concentração de interesse em nosso trabalho, a razão de concentração atômica O/Si obtida por RBS correlaciona-se linearmente com o índice de refração. As intensidades e posições dos picos de PL e as curvas de histereses observadas através de medidas C-V, após os tratamentos térmicos, dependem das razões de fluxo O2/SiH4 utilizadas na deposição. Observamos que temperatura e tempo de tratamento térmico têm forte influência nas propriedades de PL das amostras selecionadas. No entanto, a influência destes parâmetros sobre as propriedades elétricas (C-V) não é tão significativa, principalmente para temperaturas de tratamentos acima de 1000 ºC. As propriedades de PL e C-V puderam ser relacionadas com a presença de nanoestruturas de silício imersas nos filmes SRSO, sendo que defeitos do tipo NBOHC e ODC, típicos do óxido de Si, também têm influência sobre essas propriedades. Comparando os dados de PL e FTIR de nossas amostras, bem como dados da literatura, concluímos que a cristalinidade das nanoestruturas de Si tem forte influência sobre a intensidade de PL. Por outro lado, a cristalinidade influencia muito pouco na capacidade de armazenamento de carga, como verificado pelas curvas de histerese nas medidas C-V. Assim, as características ópticas e elétricas de nossas amostras estão associadas principalmente à presença de nanoestruturas de silício dentro da matriz de óxido de Si. Nossas amostras demonstram alta potencialidade para aplicação em dispositivos optoeletrônicos e nanoeletrônicos. / Abstract: In this work we have analyzed samples of Silicon Rich Silicon Oxide (SRSO) obtained by an Electron Cyclotron Resonance Chemical Vapor Deposition system (ECR-CVD). Structural, compositional, electrical and optical properties were investigated by Fourier transform infrared (FTIR), transmission electron microscopy (TEM), Rutherford backscattering spectroscopy (RBS), capacitance-voltage (C-V), photoluminescence (PL) and ellipsometry. By fitting a long range refractive indices curve as a function of O2 flow, it can be seem that the ECR-CVD system is able to produce films with high control on the refractive indices, which, indirectly, suggest the possibility of control of the optical and electrical characteristics, since all these characteristics are dependent of Si concentration in the film, as refractive index. Into the region of interest for our work, the atomic concentration ratio O/Si obtained by RBS correlates linearly with the refractive indeces. The PL intensities and peak positions and the hysteresis curves observed by C-V characterizations, after thermal treatments, show dependence on O2/SiH4 flow ratios used in the work. We observed that temperature and time of thermal treatments have strong influence on PL properties of the selected samples. Nevertheless, the influence of these same parameters on electrical properties (C-V) are less significant than for PL properties, mainly for temperatures above 1000 oC. The PL and CV characteristics of our samples can be related to the presence of silicon nanostructures embedded inside SRSO films. On the other hand, typical silicon oxide defects, like NBOHC and ODC, have some influence on such optical and electrical properties. Comparing our PL and FTIR data, as well as data from literature, we can suppose that crystallinity has strong influence on PL intensity. On the other hand, crystallinity has just a weak influence on the charge storage capacity of our samples, as we had seen by the hysteresis curves in C-V measurements for samples treated at 1100 oC and 1150 oC. Finally, we conclude that optical and electrical characteristics of our samples are associated principally to the presence of silicon nanostructures embedded in a silicon oxide matrix. Our samples showed high potentiality to applications as optoelectronic and nanoelectronic devices. / Doutorado / Eletrônica, Microeletrônica e Optoeletrônica / Doutor Engenharia Elétrica
694

Propriedades ópticas de vidros de fluoretos de indio e zircônio puros e dopados com Nd ou Pr. / Optic properties of indium and zirconium fluoride glasses pure and doped with Nd or Pr.

Celso Xavier Cardoso 13 October 1992 (has links)
Neste trabalho apresentamos uma nova classe de vidros de fluoretos de metais pesados (HMF) baseados nos fluoretos de índio (InF3) de composição InSrBaZnGdNa e InSrBaZnGaNa. Realizamos um estudo das propiredades físicas (tais como: índice de refração, temperaturas características e estabilidades) e óticas (absorção, emissão e tempo de vida) de vidros puros e dopados com Nd ou Pr. As propriedades estão comparadas com aquelas dos vidros ZrBaLaAlNa (ZBLAN). A principal característica dos vidros de fluoretos de índios puros é a extensa transmissão no IV (até 8330 nm), maiores que a do ZBLAN (até 6650 nm). Tanto os vidros dopados com Nd como com Pr são materiais promissores para o desenvolvimento de laser com emissões a 1050 e 1320 nm nos vidros de Nd e a 1320 nm no vidro com Pr e amplificadores óticos para telecomunicações na janela ótica centrada a 1300 nm, uma vez que apresentam bandas de emissão a 1315 nm (InSBZnGdN), 1317 nm (InSBZnGdN:Nd) e a 1320 nm (InSBZnGdN:Pr). / We present a new class of heavy metals fluoride glasses (HMF) of InSrBaZnGdNa and InSrBaZnGaNa compositions. We have realized a study of the physical properties such as refraction index, characteristic temperatures, stability and optical properties such as absorption, emission, lifetime of pure, Nd or Pr doped glasses. These properties are similar to those obtained for glasses of ZrBaLaAlNa (ZBLAN) composition. The main characteristic of pure indium fluoride glasses is their larger transmission window in the infrared region (8330 nm) compared to ZBLAN composition (6650 nm). Rare earth doped glasses are promising materials for the development of glasses laser with emission in the 1050-1320 nm range (Nd) and 1320 nm (Pr), as well as optical amplifiers for telecommunication in the optical window centered at 1300 nm, as prominent emission bands are located at 1315 nm (InSBZnGdN), 1317 nm (InSBZnGdN:Nd) and 1320 nm (InSBZnGdN:Pr).
695

Interação entre portadores e íons magnéticos em poços quânticos de InGaAs/GaAs:Mn / Interaction between carriers and magentic ions in quantum wells of InGaAs/GaAs:Mn

González Balanta, Miguel Ángel, 1985- 12 April 2014 (has links)
Orientador: Maria José Santos Pompeu Brasil / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-25T21:17:06Z (GMT). No. of bitstreams: 1 GonzalezBalanta_MiguelAngel_D.pdf: 5068966 bytes, checksum: c4aafc0a3e660efae9cc987f6dd987e5 (MD5) Previous issue date: 2014 / Resumo: Neste trabalho investigamos a interação entre portadores confinados em poços quânticos de InGaAs/GaAs e íons de Mn de uma dopagem tipo delta na barreira do poço. Utilizamos como base para este estudo dois tipos de estruturas. O primeiro tipo tem apenas a dopagem tipo delta de Mn e o segundo tipo, inclui duas camadas de dopagem tipo delta nas duas barreiras do poço, sendo uma dopagem de C e a outra de Mn. Observamos que a assimetria das estruturas devido às dopagens se reflete na interação dos portadores confinados com os íons de Mn. Os resultados indicam que esta interação se torna relativamente mais forte no conjunto de amostras com dopagem assimétrica apenas de Mn. Em nossa investigação, utilizamos diversas técnicas ópticas como fotoluminescência, fotoluminescência de excitação e fotoluminescência resolvida no tempo, incluindo análises da polarização da luz emitida e efeitos de campo magnético. Apesar da separação espacial entre os íons de Mn e os portadores confinados no poço, observamos vários efeitos que associamos a interação entre estas entidades. Observamos uma significativa amplificação da intensidade da força de oscilador de transições proibidas do poço em estruturas dopadas apenas com Mn. Este efeito foi interpretado como uma possível indicação da formação de polarons magnéticos ligados. Nas medidas com campo magnético, vimos que o grau de polarização dos portadores apresenta uma componente associada à presença dos íons de Mn. Esta componente, dominante apenas a baixos campos magnéticos, segue uma função tipo Brillouin associada a sistemas ferromagnéticos. Dependendo do perfil da estrutura, esta componente pode ter seu sinal invertido, levando a uma dependência da polarização com o campo magnético anômala. Finalmente, realizamos um estudo detalhado da dinâmica de polarização dos portadores com medidas de fotoluminescência resolvida no tempo. Desenvolvemos uma técnica especial envolvendo dois feixes de laser pulsados com controle tanto da separação temporal entre seus pulsos, quanto das suas polarizações circulares, que podiam ser iguais ou invertidas. Observamos que o grau de polarização gerado por um pulso é alterado se logo antes dele (centenas de pico-segundos), a amostra é excitada com pulso com polarização invertida. Associamos este efeito a um tipo de memória de polarização relacionada com a magnetização óptica dos íons de Mn. Assim, a excitação com luz circularmente polarizada gera portadores com spin preferencial, que atuam sobre os íons magnéticos, e que por sua vez afetam a polarização dos próprios portadores, agindo como um reservatório de polarização devido aos tempos de spin relativamente mais longos dos íons de Mn. Notamos que os efeitos mencionados acima são consideravelmente mais fortes no conjunto de amostras apenas com dopagens de Mn que devem apresentar um perfil de potencial mais assimétrico. Também obtivemos resultados consistentes que demonstram que estes efeitos tendem a diminuir quando a quantidade de Mn na camada delta é reduzida, quando a separação entre a camada delta de Mn e o poço quântico é aumentada, e quando aumentamos a temperatura do sistema. Em especial, os efeitos tendem a desaparecer para temperaturas em torno de 60 K, consistente com os valores da temperatura de Curie obtida para amostras similares / Abstract: In this work we investigated the interaction between confined carriers in of InGaAs/GaAs quantum wells (QWs) and Mn ions from a Mn delta-doping at the barrier of the QW. We have used two types of structures in this study. Samples of the first type have only a Mn delta-doping at the QW barrier, while samples from the second type include an additional C delta-doping layer at the other barrier. We found that the asymmetry of the structures due to doping is reflected in the interaction of carriers confined in the well and the Mn ions. The results indicate that this interaction becomes relatively stronger in the set of samples with asymmetrical doping of Mn solely. In our research, we have performed continuous-wave photoluminescence (CW-PL), excitation photoluminescence (CW-PLE), time-resolved photoluminescence (TR-PL), including analysis of the polarization of the emitted light and effects of a magnetic field. Despite the spatial separation between the Mn ions and the carriers confined in the QW, we observed various effects attributed to the interaction between these entities. We observed a significant enhancement of the intensity of the oscillator strength from transitions that are prohibited for symmetric QWs for the Mn doped structures. This effect was interpreted as a possible indication of the formation of bound magnetic polarons (BMP). In the measurements under a magnetic field, we observed that the degree of polarization of the carrier has a component associated with the presence of Mn ions. This component dominates the polarization under small magnetic fields and follows a like-Brillouin function associated to ferromagnetic systems. Depending on the profile of the structure, this component may have its sign reversed, leading to an anomalous polarization dependency with magnetic field. Finally, we performed a detailed study of the dynamics of the polarization of the carriers with time-resolved photoluminescence. We have developed a special technique involving two pulsed beams with a variable time-delay and individually-controlled circular-polarizations, which could be equal or reversed. We observed that the degree of polarization generated by a pulse is changed if just before it (hundreds of pico seconds) the sample was excited with a pulse with reversed polarization. We associated this effect to a kind of polarization memory related to the optical magnetization of Mn ions. Therefore, the excitation with circularly-polarized light generates carriers with a preferential spin that might act on the magnetic ions. In turn, the polarized Mn ions must affect the spin-polarization of the carriers, acting as a reservoir of the polarization, due to the relatively longer spin times of the Mn ions. We noticed that all these effects are considerably stronger for the set of samples doped only with Mn, that should present a more asymmetric potential profile. We also obtained consistent results revealing that all these effects tend to decrease when the amount of Mn in the delta-layer is reduced, when the separation between the Mn layer and the QW is increased, and when we increase the temperature of the sample. In particular, the effects tend to disappear at temperatures around 60 K, in accordance with the Curie temperature found for similar samples / Doutorado / Física / Doutor em Ciências
696

Material properties of ZnO thin films prepared by spray pyrolysis

van Heerden, Johannes Lodewikus 16 August 2012 (has links)
Ph.D. / In the search to improve the conversion efficiency of solar cells such as α-Si and CuInSe2 cells, attention have recently been focused on the use of transparent conducting oxides (TCO's) as window layers and top electrodes in these cells. Materials such as indium tin oxide (ITO) and fluorine-doped tin oxide (FTO) thin films were used due to their excellent electro-optical properties, but it was found that they were unstable when subjected to a hydrogen plasma (during the a-Si deposition) and that the materials reduced to their metallic forms, degrading their electrical and optical properties. Zinc oxide (ZnO), however, possess electrical and optical properties equal to ITO and FTO, but is stable in the presence of a hydrogen plasma. In this study a system for the deposition of ZnO thin films by spray pyrolysis was developed and the films successfully deposited. The films were also doped with A1C1 3 in an attempt to further improve the films' conductivities. The films were then characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), electrical measurements (Hall and four-point probe measurements) and optical analyses of the films. The films were compared with films deposited by atomic layer epitaxy (ALE) and DC sputtering. It was found that the films were crystalline with a predominantly (002) preferred orientation. The addition of Al as dopant, however, resulted in the film structure deteriorating. The SEM micrographs obtained of the films indicated films with a close-packed structure, existing of small grains and the film surface having a textured appearance. It was further found that the deposition parameters of the films influenced both the structures of the films and the morphologies and the micrographs indicated that the addition of Al as dopant resulted in the film formation being inhibited and even resulting in no proper film being deposited. It was found that the as-deposited ZnO films were resistive and that the films had to be subjected to a post-deposition annealing to decrease the film resistivity. The annealing conditions were investigated and it was found that annealing the films in hydrogen at their deposition temperature for an hour resulted in the largest decrease in the films' resistivities, typically two orders of magnitude. Studies of the substrate temperature indicated that the films had to be deposited at between 350 and 420°C and that a reduction in the substrate temperature resulted in the film resistivity increasing. Contrary to literature, it was found that the addition of Al as dopant had no beneficial influence on the electrical properties of the films and that dopant concentrations exceeding 1.0 at.% resulted in the film resistivity increasing. The films were characterized optically by analysing the transmission spectra obtained of the films, using the envelope technique. It was found that the films had transmissions exceeding 95% and that the refractive indices and optical gaps centred around 1.99 and 3.3 eV respectively. Both properties were affected by the deposition parameters. The ZnO films deposited by spray pyrolysis compared excellently with the films prepared by ALE and DC sputtering in all aspects. It is hence clear that ZnO films, with characteristics suitable for solar cell application, can be deposited by the simple and inexpensive technique of spray pyrolysis.
697

Influence des propriétés optiques et de l'endommagement de barrières thermiques EB-PVD pour la mesure d'adhérence par choc laser LASAT-2D / Influence of optical properties and of the damaging of EB-PVD thermal barrier coatings for the measurement of adhesion by laser shock LASAT-2D

Fabre, Grégory 09 December 2013 (has links)
Les barrières thermiques avec zircone EB-PVD pour les turbines aéronautiques sont soumises à des conditions extrêmes qui conduisent à l'écaillage du dépôt. La prévention de leur endommagement est donc nécessaire pour assurer l'intégrité des pièces. Afin de comprendre et de reproduire leur évolution dans une turbine, les barrières thermiques actuelles sont soumises à des essais longs de cyclage thermique. L'essai LASAT est un essai d'adhérence rapide à mettre en oeuvre qui se place en complément du cyclage thermique. L'impulsion laser appliquée sur la face nue de l'AM1 génère une onde de choc de compression qui se propage jusqu'à la surface libre de la zircone. La réflexion forme une onde de traction qui effectue le trajet inverse et peut rompre les interfaces qu'elle traverse. Le décohésion génère une tache blanche dans la zircone directement visible à l'oeil. Ce phénomène optique est élucidé en relation avec la microstructure de la zircone et la présence d'une fissure à l'interface. Pour connaitre le potentiel de l'essai, une large gamme d'échantillons avec différentes orientations du superalliage, quatre préparations de sous-couche, cinq microstructures de zircone et deux vieillissements thermiques ont été utilisés.Leur caractérisation a permis de les classer et de comparer leurs évolutions et leurs endommagements par cyclage thermique ou par LASAT. Le dimensionnement des fissures interfaciales par des méthodes non destructives a été réalisé par piézospectroscopie en exploitant les cartographies associées au signal defluorescence, par profilométrie et à partir de la tache blanche. Une approche simple et innovante exploitant et optimisant le comportement optique de la zircone est mise en place. Les tailles des fissures relevées ont mis en évidence le rôle des ondes 2D et permis la réalisation de l'essai LASAT-2D. Ici, ce n'est plus l'apparition de la fissure qui est recherchée, mais sa taille qui peut directement informer de l'adhérence à partir d'un seul choc laser. La modélisation numérique a confirmé le rôle de ces ondes 2D et leur potentield'utilisation par des abaques LASAT-2D. Ces courbes permettent de distinguer différentes préparations de barrières thermiques brutes d'élaboration ou vieillies. Un protocole complet est ainsi fourni pour le contrôle, la mesure et le suivi de la tenue mécanique de barrières thermiques sur des éprouvettes usuelles industrielles. Dans des essais complémentaires, le LASAT-2D a été appliqué en "face avant", avec le choc coté zircone, sur des éprouvettes et des pièces industrielles. Les mêmes tendances que pour le LASAT-2D développé dans cette thèse sont observées. Ceci autorise la perspective de l'application de cet essai et de cette méthodologie sur des formes complexes et fermées, telles les aubes de turbine. / EB-PVD thermal barrier coatings used in aircraft turbines are subjected to extreme conditions that lead to their spallation. To ensure the integrity of the parts, it's necessary to prevent coating damages. In order to understand and reproduce their evolution in a turbine, current thermal barrier coatings are subjected to long thermal cycling. The LASAT is a rapid adhesion test that could complement the thermal cycling. The laser pulse applied to the AM1 face generates a compressive shock wave which propagates towards the free surface of the zirconia. The reflection of this wave generates a tensile shock wave which can damage the interface and create a white spot in zirconia top coat. To determine the potential of the test, a wide range of samples with different superalloy orientations, bondcoat preparations, zirconia microstructures and thermal aging were used. Characterizations were carrying out to classify and compare their evolution and their damage by thermal cycling or LASAT. The size of interfacial cracks by non-destructive tests was achieved by piezospectroscopie maps associated with the fluorescent temporal signal, by profilometry and from the white spot. A simple and innovative approach by optimizing the optical behavior of zirconia is developed. These results highlight the role of 2D waves and allow the realization of the testLASAT-2D. Here, it is not the appearance of the crack that is looking for, but its size, which can directly inform about the mechanical adhesion from a single laser shock. Numerical modeling has confirmed the influence of 2D shock waves and their potential using LASAT-2D charts. These curves are used to distinguishdifferent preparations of thermal barrier coatings as produced and after thermal aging. A complete protocol is thus provided for monitoring, measuring and determine the interface strength of thermal barrier coatingson industrial specimens. On further testing, LASAT-2D was applied directly on the coating of specimens and industrial parts. The same results as for the 2D-LASAT developed in this thesis are observed. This allows the prospect of the application of this test and the methodology on complex and closed shapes, suchas turbine blades.
698

Matériaux moléculaires à propriétés optique et magnétique à base de complexes métalliques polynucléaires : Thiacalixarènes/métaux de transition / Molecular materials made of metallic polynuclears complexes with optical and magnetic properties : Thiacalixarenes / metals of transition

Lamouchi, Meriam 21 December 2012 (has links)
La conception et la réalisation d’architectures moléculaires de type [Mx(μ-L)yL’z]n, où μ-L est un ligand pontant, L’ un ligand terminal, n la charge et M un ion métallique de transition, sont attrayantes de part leurs richesses dans le domaine de la chimie de coordination mais aussi pour leurs applications potentielles dans des domaines tels que le magnétisme, l’optique ou encore la catalyse. Le ligand terminal qui a été choisi pour ce travail est un macrocycle, appelé p-tert-butylsulfonylcalix[4]arène, formé d’unités phénoliques reliées entre elles par des groupements sulfonyle. Dans un premier temps, une famille de complexes tétranucléaires de Mn2+ a été obtenue et caractérisée. Ces agrégats ont présenté des propriétés optiques de luminescence originales, à l’état solide et en solution. La photo-réaction, en solution de ces clusters, a permis de mettre en évidence le premier complexe stable mononucléaire de Mn3+/p-tert-butylsulfonylcalix[4]arène. La photo-réactivité de ces complexes, a révélé pour la première fois, la dynamique moléculaire que ce ligand pouvait avoir sous une excitation lumineuse. Puis, les réactions faites avec l’ion Mn2+ ont été transposées sur l’ion Co2+. La réactivité différente de cet ion, a permis d’isoler différents agrégats de structures moléculaires originales. Certains ont présenté des propriétés de « single ion magnet » (SIM). Enfin, des études sur la modification du p-tert-buytlthiacalix[4]arène ont débouché sur la mise au point de la première méthode générale de mono-O-alkylation de ce type de macrocycle. / The realization of molecular architectures type [Mx(μ-L)yL’z]n; (with μ-L a chelating ligand, L’ a terminal ligand, n a charge and M a metallic transition ion) are attractive because of their potential applications in many domains such as magnetism, optics and catalysis.The terminal ligand which was chosen for this work is a macrocycle, called p-tert-butylsulfonylcalix[4]arene formed by phenolic units connected between them by sulfonyle groups.Firstly, a family of tetranuclear manganese (II) complexes was obtained and characterized. These clusters presented original optical properties of luminescence, in solid state and in solution.In solution, the photo-reaction of these clusters allowed to obtain the first stable ever mononuclear complex Mn3+/p-tert-butylsulfonylcalix[4]arene. Photo-reactivity of these complexes revealed that this ligand could have a molecular dynamics under a light irradiationThen the reactions made with ions Mn2+ were transposed for ions Co2+. Reactivity of Co2+ allowed to isolate various clusters with original molecular structures. Some presented properties of “Singles Ions Magnets”Finally, studies on the modification of p-tert-butylthiacalix[4]arene enabled us to design the first general method of mono-O-alkylation of this macrocycle type.
699

Gram quantities of silver and alloy nanoparticles: synthesis through digestive ripening and the solvated metal atom dispersion (SMAD) method: antimicrobial properties, superlatteic[i.e. super lattice] selfassembly, and optical properties

Smetana, Alexander B. January 1900 (has links)
Doctor of Philosophy / Department of Chemistry / Kenneth J. Klabunde / This is an account of the synthesis of several drastically different forms of silver nanoparticles: Bare metal nanoparticles, dry nanoparticulate powders, aqueous soluble particles, and organic ligand coated monodisperse silver nanoparticles were all produced. The synthetic method was adapted from previous studies on gold nanoparticles and investigated to understand the optimal conditions for silver nanoparticle synthesis. Also the procedure for refinement of the nanoparticles was studied and applied to the formation of alloy nanoparticles. This extraordinary procedure produces beautifully colored colloids of spherical metal nanoparticles of the highest quality which under suitable conditions self-assemble into extensive three dimensional superlattice structures. The silver nanoparticle products were later tested against several biological pathogens to find dramatic increases in antimicrobial potency in comparison to commercially available silver preparations.
700

Theoretical Studies Of Electronic And Optical Properties Of Some Heteroconjugated Systems

Jha, Prakash Chandra 08 1900 (has links) (PDF)
No description available.

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