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The advent of ultrafast lasers has enabled micromachining schemes that cannot be achieved by other current techniques. Laser direct writing has emerged as one of the possible routes for fabrication of optical waveguides in transparent materials. In this thesis, the advantages and limitations of this technique are explored. Two extended-cavity ultrafast lasers were built and characterized as the laser sources for this study, with improved performance over existing systems. Waveguides are fabricated in oxide glass, chalcogenide glass, and polymers, these being the three major classes of materials for the telecommunication industry. Standard waveguide metrology is performed on the fabricated waveguides, including refractive index profiling and mode analysis. Furthermore, a finite-difference beam propagation method for wave propagation in 3D-waveguides is proposed. The photo-structural modifications underlying the changes in the material optical properties after exposure are investigated. The highly nonlinear processes of the light/matter interaction during the writing process are described using a free electron model. UV/visible absorption spectroscopy, photoluminescence spectroscopy and Raman spectroscopy are used to assess the changes occurring at the atomic level. Finally, the impact of laser direct writing on nonlinear waveguide applications is discussed.

In this study unintentionally doped GaN grown by hydride vapor phase epitaxy that exhibits a sharply delimited region of green color was investigated. Optical analysis was performed by absorption and photoluminescence spectroscopy. An absorption band between 1.5 and 2.0 eV was found to be responsible for the green color and was related to a sharp emission at 1.193 eV by luminescence and excitation spectroscopy. The appearance of both optical signatures in the region of green color was related to an increase of Cr contamination detected by secondary ion mass spectrometry. We propose that the origin of green color as well as the emission line at 1.193 eV is attributed to internal transitions of Cr⁴⁺.

This thesis is concerned with the influence of nanoscale boundaries and interfaces upon the electronic processes that occur within both organic and inorganic semiconductors. Photoluminescent polymers, highly conducting polymers and nanoscale inorganic semiconductors have been investigated using state-of-the-art ultrafast optical techniques, to provide information on the sub-picosecond photoexcitation dynamics in these systems. The influence of dimensionality on the excitation transfer dynamics in a conjugated polymer blend is studied. Using time-resolved photoluminescence spectroscopy, the transfer transients both for a three-dimensional blend film, and for quasi-two-dimensional monolayers formed through intercalation of the polymer blend between the crystal planes of a SnS2 matrix have been measured. A comparison of the experimental data with a simple, dimensionality-dependent model is presented, based on point dipole electronic coupling between electronic transition moments. Within this approximation, the energy transfer dynamics are found to adopt a three-dimensional character in the solid film, and a two-dimensional nature in the monolayers present in the SnS2 -polymer nanocomposite. The time-resolved conductivity of isolated GaAs nanowires has been investigated by optical-pump terahertz-probe time-domain spectroscopy. The electronic response exhibits a pronounced surface plasmon mode that forms within 300 fs, before decaying within 10 ps as a result of charge trapping at the nanowire surface. The mobility has been extracted using the Drude model for a plasmon and is found to be remarkably high, being roughly one third of that typical for bulk GaAs at room-temperature and indicating the high quality and low bulk defect density in the nanowires studied. Finally, the time-resolved conductivity dynamics of photoexcited polymer-fullerene bulk heterojunction blends for two model polymers, P3HT and MDMO-PPV, blended with PCBM are presented. The observed terahertz-frequency conductivity is characteristic of dispersive charge transport for photoexcitation both at the π−π* absorption peak (560 nm for P3HT), and significantly below it (800 nm). The photoconductivity at 800 nm is unexpectedly high, which is attributed to the presence of a charge transfer complex. In addition, the excitation-fluence dependence of the photoconductivity is studied over more than four orders of magnitude. The time-averaged photoconductivity of the P3HT:PCBM blend is over 20 times larger than that of P3HT, indicating that long-lived positive polarons are responsible for the high photovoltaic efficiency of polymer:fullerene blends. At early times (~ ps) the linear dependence of photoconductivity upon fluence indicates that interfacial charge transfer dominates as an exciton decay pathway, generating charges with mobility of at least ~0.1cm2 V−1 s−1. At later times, a sub-linear relationship shows that carrier-carrier recombination effects influence the conductivity on a longer timescale (> 1 μs).

Polycrystalline Zn1-xCrxO (0.01 ≤ x ≤ 0.09) samples synthesized by solid state reaction technique were sintered at different temperatures following slow step sintering schedule. Structural, micro-structural, optical, magnetic properties and homogeneity were investigated using suitable characterisation techniques. Cr2O3 and CrO2 phases have been detected in the XRD patterns and Raman spectra of Zn1-xCrxO samples with x ≥ 0.05. Photoluminescence study has indicated improved optical property of the samples compared to undoped ZnO. While low percentage Cr doped samples showed diamagnetic behaviour, higher percentage doped samples (≥ 5%) exhibited ferromagnetic, paramagnetic and anti-ferromagnetic behaviours depending upon the sintering temperatures. The magnetic properties have been analysed through Electron Spin Resonance study. A g-value of 1.97 indicates Cr in +3 valence state in doped ZnO system. Presence of Cr3+ and Cr4+ in ZnO is understood to facilitate super exchange interactions to promote ferromagnetism at room temperature. ESR study shows improved magnetic homogeneity achieved by slow step sintering process. / Physics / M. Sc. (Physics)

Made available in DSpace on 2016-06-02T19:02:44Z (GMT). No. of bitstreams: 1 6412.pdf: 14036212 bytes, checksum: dc6e90045bca1050bc9fd76f94f1f30a (MD5) Previous issue date: 2014-06-30 / Financiadora de Estudos e Projetos / The increase in the production of antimicrobial metabolites by Paenibacillus polymyxa RNC-D was appraised through the study of cultivation variables. Two process variables, namely the glucose and inoculum concentrations, were evaluated in different levels (5 to 40 g/l, and 2.5% to 5.0% v/v, respectively), and their effects on biomass formation, minimal inhibitory concentration (MIC) against Escherichia coli and surface tension reduction (STR) were studied. The fermentation process was firstly carried out using non-optimized parameters, where the dependent variables biomass, MIC and STR reached the values of 0.6 g/l, 1.000,0 μg/ml and 18.4 mN/m, respectively. The optimum glucose (16 g/l) and inoculum concentrations (5.0% v/v) were defined in order to maximize the biomass formation, with low value of MIC and large STR of extract. Under these conditions, a biomass of 2.76 g/l, MIC of 15.8 μg/ml, and STR of 14.58 mN/m were predicted by the model. Data attained by experiments using optimized settings showed the following values: biomass 2.05 g/l; MIC 31.2 μg/ml; STR 10.7 mN/m. Thus, the percentage of improvement for each target response was: biomass 241.6%; MIC 96.88%; STR 41.85%. It was found that high concentrations of glucose substrate, although reflected in an increase in bacterial biomass, inhibited the microbial secondary metabolism, resulting in a low production of biomolecules associated with high values of MICs. Thus, initial concentrations of glucose and inoculum are shown as variables of strong influence in the production of antimicrobial metabolites by P. polymyxa RNC-D. Through the methods of experimental factorial design and surfaceresponse followed by graphical optimization it was possible to determine the optimum operating condition to achieve both maximum biomass and RTS as well as and lowest possible values of CIM. The validity of the proposed model was verified and confirmed. This is the first study on the optimization of culture conditions for the production of antimicrobial metabolites by P. polymyxa RNC-D, and constitutes an important step in the development of strategies to modulate the production of antimicrobial molecules by this microorganism in elevated levels. Novel antimicrobial compounds were isolated from the fermentation broth of P. polymyxa RNC-D, here named total extract (TE). It was possible to verify the presence of lipopeptide and peptide active compounds through enzymatic assays made with ET. Total extract was subjected to a two-phase system, resulting in lipopeptide extract (LPE) and aqueous fraction (AF). According to the results of bioassays, LPE has broad-spectrum activity against Gram-positive bacteria, Gram-negative bacteria and fungi. The mass spectrometry analysis of PLA revealed the existence of a novel compound that was named polycerradin. The purification of a novel antimicrobial peptide (AMP) from the AF was carried out by using chromatography. The compound was active against Gram-negative bacteria. Nterminal analysis determined the amino acid sequence, as well as MS / MS analysis confirmed the primary structure of this new compound. This research reports firstly the production of PAM PpRNCD that has an unusual amino acid in its constitution. It is an unprecedented fact considering the bacterial specie P. polymyxa. In terms of molecule size, PAM PpRNCD can be considered one of the smallest active natural peptide reported to date. It was also possible to isolate from FA the depsipeptides IL-F04a (m/z 883), LI-F04b (m/z 897), LI-F03a (m/z 947) and LI-F03b (m/z 961) previously described in the literature. The photoluminescence study of the LPE, TE, AF in both at room temperature (RT) and low temperature (T = 8K) was performed. In addition, this technique was applied to evaluate the action of the ELP on Staphylococcus aureus ATCC 29213, Enterococcus faecalis ATCC 29212, Escherichia coli ATCC 29212, Shigella sonnei ATCC 1578 and Candida albicans ATCC 10231 in two different situations: (a) immediately after mixing LPE with the bacterial and fungus cell suspension, and (b) after thirty minutes. The photoluminescence emission was collected by a triple spectrometer (three diffraction gratings) T64000 model from Jobin Yvon, equipped with an optical microscope. For the detection of the radiation emitted by the sample we used a CCD camera (charge coupled device) cooled by liquid nitrogen. The slits of the spectrometer were adjusted to produce a spectral resolution of the order of 10-4 nm. The excitation source used was the line of 457 nm (violet) from an argon laser. The behaviors here observed indicate a strong potential for applications in biosensors as well as molecular markers. / Através do estudo de variáveis do cultivo pretendeu-se aumentar a produção de metabólitos antimicrobianos por Paenibacillus polymyxa RNC-D. Duas variáveis do processo - glicose e concentração de inóculo - foram avaliadas em diferentes níveis e seus efeitos na formação de biomassa, concentração inibitória mínima (CIM) contra Escherichia coli e redução na tensão superficial (RTS) foram estudados. Utilizando parâmetros não-otimizados as variáveis dependentes biomassa, CIM e RTS atingiram valores de 0,6 g/l, 1.000,0 μg/ml e 18,4 mN/m, respectivamente. As concentrações ótimas de glicose (16 g/l) e inóculo (5,0% v/v) foram definidas no sentido de maximizar a formação de biomassa e RTS do extrato, bem como diminuir o valor de CIM do extrato. Experimentalmente 2,05 g/l de biomassa; 31,2 μg/ml de CIM e 10,7 mN/m de RTS foram obtidos sob condições otimizadas. Foi constatado que altas concentrações do substrato glicose, embora refletissem em aumento de biomassa bacteriana, inibiram o metabolismo secundário microbiano, resultando em baixa produção de biomoléculas associada a altos valores de CIM. Através dos métodos de design fatorial experimental e superfície-resposta seguidos por otimização gráfica foi possível determinar a condição operacional ótima das concentrações iniciais de glicose e inóculo, as quais se demonstraram como variáveis de grande influência na produção de metabólitos antimicrobianos por P. polymyxa RNC-D. O extrato total (ET), proveniente do caldo de fermentação de P. polymyxa RNC-D, foi utilizado para pesquisa e isolamento de novos compostos antimicrobianos. Através de ensaios enzimáticos feitos com ET foi possível verificar a natureza lipopeptídica e peptídica dos compostos antimicrobianos. O ET foi submetido a um sistema de duas fases, separandose então em extrato lipopeptídico (ELP) e fração aquosa (FA). Resultados de bioensaios revelaram que o ELP apresenta amplo espectro de atividade contra bactérias Grampositivas, Gram-negativas e fungo. A análise por espectrometria de massas de ELP revelou a presença de um composto peptídico inédito o qual foi denominado polycerradin. A partir da fração aquosa (FA) foi possível a purificação de um novo peptídeo antimicrobiano (PAM) através de etapas cromatográficas. A bioatividade do composto foi avaliada e confirmada frente às bactérias Gram-negativas. A determinação da sequência de aminoácidos foi realizada por análise do N-terminal, e a confirmação da estrutura primária deste novo composto foi feita por MS/MS. O presente estudo relata pela primeira vez a produção do PAM PpRNCD que possui um aminoácido não usual em sua constituição, relato primeiramente aqui descrito considerando-se a espécie bacteriana P. polymyxa. Em termos de tamanho de molécula, pode-se considerar que o PAM PpRNCD é um dos menores peptídeos naturais ativos relatados até o momento. Utilizando-se a FA também foi possível o isolamento dos depsipeptídeos LI-F04a (m/z 883), LI-F04b (m/z 897), LI-F03a (m/z 947) e LI-F03b (m/z 961) previamente descritos na literatura. O estudo da fotoluminescência do ELP, do ET e da FA foi realizado tanto em temperatura ambiente (RT) quanto em baixa temperatura (T=8K). Também se estudou, através desta técnica, a ação do ELP sobre as bactérias Staphylococcus aureus ATCC 29213, Enterococcus faecalis ATCC 29212, Escherichia coli ATCC 29212, Shigella sonnei ATCC 1578 e fungo Candida albicans ATCC 10231 em duas situações: (a) imediatamente após a mistura do ELP com a suspensão celular bacteriana, e (b) trinta minutos após a mistura. Detectou-se emissão fotoluminescente por ELP, ET e FA, e sinais de Raman a λ 699 nm (FA a baixa temperatura). Decorridos 30 min da mistura do ELP com as suspensões celulares microbianas houve alteração na emissão fotoluminescente, sendo que alguns sinais foram suprimidos (λ 470, 480 e 700 nm para S. sonnei, por exemplo). Isto evidencia a potencial aplicação destas frações (ELP, ET e FA) para a fabricação de sensores, detectores e marcadores moleculares.

>Magister Scientiae - MSc / In this study PbSe quantum dots (QDs) were successfully synthesized via the organometallic and aqueous routes. Optical characterization was carried out using photoluminescence (PL) spectroscopy, structural and morphological characterization were carried out using X-ray diffraction (XRD) and transmission electron microscopy (TEM). Energy-dispersive X-ray spectroscopy (EDS) was used to determine the composition of the QDs. All the synthesized QDs were found to have emissions within the near-infrared region of the spectrum (≥1000 nm) with most of them being less than 5 nm in size. The aqueous synthesized QDs had a perfect Gaussian emission spectrum with a FWHM of ~23 nm indicating pure band gap emission and narrow size distribution respectively. The QDs were determined to have a cubic rock-salt crystal structure consistent with bulk PbSe. The aqueous synthesized QDs were however not stable in solution with the QDs precipitating after approximately 48 h. The organometallic synthesized QDs were transferred into the aqueous phase by exchanging the surface oleic acid ligands with 11-mercaptoundecanoic acid ligands. The ligand exchanged QDs were however stable in solution for over two weeks. The effects of reaction parameters on the optical and structural properties of the organometallic synthesized QDs were investigated by varying the reaction time, temperature, ligand purity, lead and selenium sources. It was observed that larger QDs were formed with longer reaction times, with reactions proceeding faster at higher reaction temperatures than at lower temperatures. Varying the ligand purity was found to have minimal effects on the properties of the synthesized QDs. The lead and selenium sources contributed largely to the properties of the QDs with lead oxide producing spherical QDs which were smaller compared to the cubic QDs produced from lead acetate. TBPSe was seen to produce smaller QDs as compared to TOPSe. The cytotoxity of the synthesized QDs was determined following the WST-1 cell viability assay with the QDs being found to be non-toxic at all the tested concentrations

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Recombination mechanisms in gallium arsenide have been studied using temperature-dependent time-resolved photoluminescence-decay. New analytical methods are presented to improve the accuracy in bulk lifetime measurement, and these have been used to resolve the temperature-dependent lifetime. Fits to temperature-dependent lifetime yield measurement of the radiative-efficiency, revealing that samples grown by the Czochralski and molecular-beam-epitaxy methods are limited by radiative-recombination at 77K, with defect-mediated nonradiative-recombination becoming competitive at 300K and above. In samples grown with both doping types using molecular-beam-epitaxy, a common exponential increase in capture cross-section characterized by a high value of E_infinity=(258 +/- 1)meV was observed from the high-level injection lifetime over a wide temperature range (300-700K). This common signature was also observed from 500-600K in the hole-lifetime observed in n-type Czochralski GaAs where E_infinity=(261 +/- 7)meV was measured, which indicates that this signature parametrizes the exponential increase in hole-capture cross-section. The high E_infinity value rules out all candidate defects except for EL2, by comparison with hole-capture cross-section data previously measured by others using deep-level transient spectroscopy. / Thesis / Doctor of Philosophy (PhD)

Ce travail s’inscrit dans le cadre d’une étude systématique des propriétés physico-chimiques de polyphosphates à l’argent permettant d’avancer sur de nouvelles voies pour les dispositifs tels que l’éclairage, les lasers accordables dans le visible, la radiophotoluminescence. L'objectif de ce travail vise la compréhension des mécanismes de luminescence de l’ion Ag+ dans les composés Na1-xAgxLn(PO3)4 (Ln = La et Y) dont la structure a été parfaitement déterminée. La luminescence des monocristaux provient des ions Ag+, dans des sites isolés et proches de lacunes positives (Ag2+) résultant de la photosensibilité aux UV pour les cristaux au lanthane. La luminescence des verres Na1-xAgxLa(PO3)4 (seuls vitrifiables) a été élucidée grâce à une étude après irradiation et à celle des verres Na2-xAgxZnP2O7. Elle est due aussi aux ions Ag+ dans des sites isolés. / This work focuses on keeping with the general pattern of investigations of physical-chemical properties of silver-polyphosphates to find new ways for devices such as lighting, visible range laser applications and radiophotoluminescence. The goal of this study aims at understanding the processes of Ag+ luminescence in Na1-xAgxLn(PO3)4 (Ln = La et Y) compounds which structure has been completely determinated. The luminescence of the single crystals is induced by Ag+ ions in isolated sites and close to hole centers (Ag2+) resulting in UV photosensitivity for the lanthanum crystals. The photoluminescence of the Na1-xAgxLa(PO3)4 glasses (glass-forming only) has been resolved owing to UV irradiation investigations and comparison with the luminescence of Na2-xAgxZnP2O7 glass. Both are also due to Ag+ ions in isolated sites.