Luminescence is the emission of light resulting from radiative transition of an atom from an excited state to a ground state. This radiative transition yields emission of photons and the luminescence is the general name which is used to classify &ldquo / cold emission&rdquo / other than the blackbody radiation. Spectroscopy involves the measurement of intensity of emitted, absorbed or scattered electromagnetic radiation as a function of wavelength. Thus, it is a valuable tool in the study of understanding the luminescence production mechanisms. Measurement of emission spectra gives information about the energy levels of transition and structure, geometry and composition of the sample. In this study, a versatile luminescence emission spectrometer was designed and developed with the main aim of measuring Photoluminescence (PL), Thermoluminescence (TL) and Optically Stimulated Luminescence (OSL) emission spectra of materials relevant for dosimetry. The spectrometer was constructed around a Littrow type monochromator by developing the necessary hardware, firmware and software. Wavelength calibration, measurement of spectral response and determination of resolution of the spectrometer were done using calibration lamps and a calibrated spectroradiometer. Finally the performance of the constructed spectrometer was tested by measuring the emission spectra of materials such as BeO, Al2O3 and CaF2 wherever possible the measured spectra were compared with the ones reported in the literature.

Pendant que la menace potentielle du bioterrorisme augmente, il y a grand besoin d'un outil qui peut détecter les agents biologiques contaminants dans l'environnement de façon rapide, fiable et précise. Par contre, les méthodes traditionnelles utilisées nécessitent l'utilisation de laboratoires d'analyse sophistiquée, souvent dans des installations centralisées, ce qui demande un capital considérable et une main-d'oeuvre hautement qualifiée. Il est possible de développé des dispositifs basés sur les biocapteurs à faible coût et très efficace à la détection d'agents biologiques. De plus, ils peuvent être utilisés dans d'autres domaines, au jour le jour, tel pour la surveillance de contaminants dans les produits comestibles. Dans le but de résoudre ce problème, une nouvelle approche pour la fabrication d'un biocapteur optique a été développée. Celui-ci serait capable de détecter, de façon directe, des micro-organismes qui seraient immobilisés à sa surface plus rapidement et plus aisément qu'avec les méthodes conventionnelles. En effet, les expériences présentées visent la fabrication d'un biocapteur suite à la déposition de molécules biochimiques sur une hétérostructure de GaAs/ALGaAs. Le biocapteur ainsi produit tire parti de la photoluminescence émise par ce semi-conducteur quantique III-V pour la détection de microorganismes immobilisés spécifiquement et négativement chargés. La présente recherche est basée sur des techniques novatrices de biocapteurs pour lesquelles il existe peu de littérature. Les travaux expérimentaux et les explications théoriques se révèlent ainsi de nature très exploratoires. Les résultats préliminaires obtenus ont d'ailleurs été similaires aux prédictions initiales. De plus, les détails théoriques et explications physiques permettent de comprendre l'origine des résultats obtenus et d'établir, de manière convaincante, les procédures à suivre pour une architecture optimale. Je rapporte ainsi l'étude de la bio-fonctionnalisation du GaAs (001) visant l'immobilisation d'anticorps polyclonaux selon deux architectures différentes. De plus, les architectures proposées ont leurs régions actives ouvertes à l'environnement, pour permettre des mesures en continues et, en plus d'être des systèmes offrant la possibilité de multiplexage, offrent un potentiel de mesures en parallèle, pour un grand nombre de mesures en simultanées. Les résultats obtenus démontrent l'immobilisation réussie ainsi que la détection effectuée du virus de l' influenza A et des bactéries Escherichia coli et Legionella pneumophila respectivement. Enfin, les avantages et les limites de chaque architecture ont ensuite été détaillés.

The demand for wide bandgap semiconductors for radiation detector applications has significantly increased in recent years due to an ever-growing need for safeguard measures and medical imaging systems amongst other applications. The need for these devices to be portable and efficient, and to operate at room temperature is important for practical applications. For radiation detectors, the semiconductor materials are mainly required to have an optimal energy gap, high average atomic number, good electrical resistivity and charge transport properties as well as purity and homogeneity. Cadmium zinc telluride (CZT) distinctly stands out among the other choices of semiconductor materials for radiation detector applications, due to its attractive material properties and the room temperature operation possibility. A tremendous amount of research is being conducted to improve CZT technology and its implementation into more commercial systems. Applications of CZT detector technology in national security, high energy physics, nuclear spectroscopy, and medical imaging systems are of special interests. However, CZT devices still face challenges that need to be understood and overcome in order to have more efficient radiation detector systems. One such challenge lies in the understanding of the surfaces of CZT detectors and surface recombination effects on charge transport, charge collection efficiency, and detector performance. Another common issue is the degradation of CZT detectors due to the presence of defects which can act as traps for the charge carriers and cause incomplete charge collection from the detectors. Thus, a major challenge is that, the commercial CZT crystals have large concentrations of defects and impurities that need to be characterized, and their effects on the detector performance should be studied. Photoluminescence (PL) spectroscopy is a sensitive, non-contact and non-destructive method, suitable to characterize lower concentrations of point defects, such as substitutional impurities (donors, acceptors) and native defects in CZT crystals. A PL spectrum provides information regarding the defect nature of the crystal by determining the presence and the type of vacancies, interstitials, and impurities in the lattice. The main objective of this thesis is to address the presence of the defects in CZT crystals, identify their types, and study their roles in the performance of x-ray radiation detectors using PL spectroscopy. Additionally, using PL method and different excitation sources including UV excitation, this thesis studies the surface of CZT samples and investigates the PL signature of the surface oxide of the samples, in an effort to optimize the surface processing and thereby improve CZT detector performance. / Graduate

De nos jours, l'augmentation des performances et la réduction des dimensions des composants microélectroniques ou optiques constituant les systèmes électroniques ou optroniques nécessite des techniques de caractérisation non destructrices, capables de sonder des micro- et nanoobjets. C'est dans cette optique que s'inscrivent les techniques de spectroscopie Raman et photoluminescence, capables de caractériser localement les contraintes mécaniques, introduites dans les dispositifs à semi-conducteurs actuels afin d'accroître leurs performances. Ce travail de thèse aborde deux objectifs, l'élargissement des capacités du spectromètre Raman polarimétrique comprenant l'ajout d'un module de détection du signal de luminescence et l'application des techniques et méthodologies développées à la caractérisation des contraintes dans des structures semiconductrices à base de silicium, germanium et arséniure de gallium. Après une étude expérimentale des paramètres pertinents, la dépolarisation, le retard et le dichroïsme, nécessaire afin de combiner le spectromètre Raman " classique " et un polarimètre, nous avons montré que l'étalonnage d'un tel système dépend de la longueur d'onde de la source d'excitation, ainsi que de la nature de la diffusion considérée (Raman ou Rayleigh). Au titre des applications de la technique, nous avons mesuré des contraintes mécaniques dans des nanolignes de silicium (15 nm d'épaisseur) et des microlignes de germanium grâce à la méthodologie de mesure développée. Les résultats obtenus ont été également modélisés analytiquement afin de mettre en évidence la physique des phénomènes observés. Ainsi, nous avons montré qu'il est possible d'amplifier le signal Raman dans les nanolignes de silicium grâce à la gestion appropriée des polarisations des rayonnements incident et diffusé. La mise en place de la technique de photoluminescence avec le contrôle des états de polarisation, rajoutée à la spectroscopie Raman, nous a permis d'étendre le champ de mesure des contraintes mécaniques dans les structures semiconductrices. Actuellement, grâce à cette technique, nous sommes capables de mesurer des efforts résiduels de l'ordre de 20 MPa, ce qui est au-delà des capacités de la spectroscopie Raman " conventionnelle " essentiellement limitée par la résolution spectrale.

In this study, silicon nanocrystals (NC) were synthesized in silicon dioxide matrix by ion implantation followed by high temperature annealing. Annealing temperature and duration were varied to study their effect on the nanocrystal formation and optical properties. Implantation of silicon ions was performed with different energy and dose depending on the oxide thickness on the silicon substrate. Before device fabrication, photoluminescence (PL) measurement was performed for each sample. From PL measurement it was observed that, PL emission depends on nanocrystal size determined by the parameters of implantation and annealing process. The peak position of PL emission was found to shifts toward higher wavelength when the dose of implanted Si increased. Two PL emission bands were observed in most cases. PL emission around 800 nm originated from Si NC in oxide matrix. Other emissions can be attributed to the luminescent defects in oxide or oxide/NC interface. In order to see electroluminescence properties Light Emitting Devices (LED) were fabricated by using metal oxide semiconductor structure, current-voltage (I-V) and electroluminescence (EL) measurements were conducted. I-V results revealed that, current passing through device depends on both implanted Si dose and annealing parameters. Current increases with increasing dose as one might expect due to the increased amount of defects in the matrix. The current however decreases with increasing annealing temperature and duration, which imply that, NC in oxide behave like a well controlled trap level for charge transport. From EL measurements, few differences were observed between EL and PL results. These differences can be attributed to the different excitation and emission mechanisms in PL and EL process. Upon comparision, EL emission was found to be inefficient due to the asymmetric charge injection from substrate and top contact. Peak position of EL emission was blue shifted with respect to PL one, and approached towards PL peak position as applied voltage increased. From the results of the EL measurements, EL emission mechanisms was attributed to tunneling of electron hole pairs from top contact and substrate to NC via oxide barrier.

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No. of bitstreams: 1 curcio_al_me_rcla.pdf: 1672370 bytes, checksum: fd59b862449a04ac385f3661da6430f3 (MD5) Previous issue date: 2016-02-29 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Nanocristais tem sido extensivamente investigados nos últimos anos devido à sua ampla gama de aplicações em vários dispositivos tais como sensores, células solares, lasers, fotocatalisadores, fotodetectores, detectores de infravermelhos, diodos emissores de luz, materiais eletroluminescentes e outros materiais emissores de luz. Semicondutores nanocristalinos apresentam propriedades eletrônicas intermediárias entre aqueles de estrutura molecular e sólidos macrocristalinos, proporcionando uma ampla gama de aplicações. Entre estes materiais, o sulfeto de zinco (ZnS) puro ou dopado tem recebido notável atenção por causa de suas propriedades estruturais ópticas, versatilidade e potencial para várias aplicações tecnológicas. O ZnS é um típico semicondutor II-VI, com um gap direto de 3,6 eV à temperatura ambiente e aproximadamente 40 meV de energia de gap, sendo um bom material luminescente utilizado em telas, sensores e lasers. Como material de gap largo, o ZnS pode facilmente hospedar diferentes metais de transição como centros luminescentes. Entre estes íons de metais de transição para estruturas dopadas, os íons Cu2+e Mn2+ são atraentes pelas emissões de luz características e por apresentarem propriedades eficientes para aplicações como luminóforos. A inserção desses íons na estrutura do ZnS proporcionam defeitos que resultam em emissão no verde para os íons Cu2+e emissão no laranja para os íons Mn2+. Neste estudo, as amostras de ZnS pura e dopadas com Cu2+ e Mn2+ foram preparados pelo método solvotermal, que demonstra ser um processo eficaz para preparar nanopartículas. Uma vez preparadas, as estruturas das amostras nanoestruturadas foram caracterizadas e correlacionada s com propriedades fotoluminescentes. Os resultados de difração de raios X mostram que as amostras de ZnS foram cristalizadas completamente sem a presença de fases secundárias e os difratogramas correspondem à estrutura blenda cúbica de zinco com grupo espacial F-43m. Os espectros de XANES (X-ray Absorption Near Edge Structure) teóricos e experimentais na borda K do Zn indicam que a incorporação de átomos de Mn na matriz ZnS causam a formação de vacâncias de Zn e S, a qual é confirmada por ajustes de espectros EXAFS (Extended X-ray Absorption Fine Structure). Estas vacâncias estão relacionadas com um desvio para o vermelho observado no pico do espectro de fotoluminescência devido a adição de Mn na estrutura do ZnS. Para o ZnS puro, o pico é centrado em ~ 504 nm, relativo as vacâncias de S na amostra nanoestruturada. À medida que se aumenta a porcentagem de Mn na matriz ZnS, uma emissão no amarelo-laranja centrada em ~ 590 nm pode ser observada, associada com a transição 4T1-6A1 no interior de níveis 3d de Mn2+. A adição de íons Cu2+ ao ZnS resulta em um alargamento no pico do espectro de fotoluminescência decorrente de emissão no azul-verde, que está relacionada a recombinação de elétrons de níveis de defeitos mais profundos dos estados t2 do Cu próximos da banda de valência. / Nanocrystals has been extensively investigated in recent years due to its wide range of applications in various devices light emitting materials such as sensors, solar cells, lasers, photocatalysts, photodetectors, IR detectors, light emitting diodes and others. Nanocrystalline Semiconductors have electronic properties between those intermediate molecular macrocristalinos and solid structure, providing a wide range of applications. Among these materials, zinc sulfide (ZnS) pure or doped has received considerable attention because of its optical structural properties, versatility and potential for several technological applications. The ZnS is a typical II-VI semiconductor with a direct band gap of 3.6 eV at room temperature and about 40 meV in energy gap, and a good luminescent material for constrution of displays, lasers and sensors. As wide band gap material, ZnS can easily host different transition metals as luminescent centers. Among these ions of transition metal doped structures, Cu2+ and Mn2+ ions are attractive for light emission characteristics and for having effective properties for applications such as phosphors. The addition of these ions in ZnS structure provide defects that result in emission in the green for the Cu2+ ions and emission in orange for the Mn2+ ions. In this study, samples of pure ZnS and doped with Cu2+ and Mn2+ ions were prepared by solvotermal method, which demonstrate to be an effective process for preparing nanoparticles. Once prepared, the structures of the nanostructured samples were characterized and correlated with photoluminescent properties. The results of X-ray diffraction showed that the ZnS samples were completely crystallized without the presence of secondary phases and XRD patterns correspond to the structure of zinc blende to cubic space group F-43m. spectra XANES (X-ray Absorption Near Edge Structure) theoretical and experimental in the Zn K edge indicates that the inclusion of Mn atoms in the ZnS matrix cause the formation of Zn and S vacancies, which is confirmed by spectral adjustments EXAFS (Extended X-ray Absorption Fine Structure). These vacancies are associated with a red shift observed in the photoluminescence spectrum peak due to the addition of Mn in ZnS structure. For pure ZnS, the peak is centered at ~ 504 nm concerning the vacancies in the S nanostructured sample. As it increases the percentage of Mn in the ZnS matrix, in yellow-orange emission centered at ~ 590 nm can be observed, associated with the transition 4 T1- 6A1 inside 3d levels of Mn2+. Adding Cu2+ to the ZnS results in a broadening of the peak of the photoluminescence spectrum due to emission in blue-green, which is related to recombination deeper defect levels of electrons of t2 Cu states near the valence band.

Nous avons élaboré des structures de quatre couches d'InN/InP (100) en enrichissant en In la surface nitrurée à l'aide d'une cellule d'évaporation calibrée. Les propriétés physiques de ces structures ont été étudiées in-situ à l'aide de spectroscopie, des électrons Auger (AES), des photoélectrons X (XPS) et UV (UPS) avant d'être analysées ex-situ par photoluminescence (PL) et mesures électriques (I(V) et C(V)). Nous avons mené une étude de PL en fonction de la température et l'évolution de l'énergie du pic de PL obtenue en fonction de la température suivait la forme en S-inversé caractéristique des effets de localisation. Les caractéristiques électriques courant-tension des structures Hg/InN/InP montrent qu'elles forment un contact Schottky. Les caractéristiques capacité-tension montrent qu'elles se comportent comme une structure lorsqu'on polarise négativement et comme une structure MIS quand on polarise positivement. Dans la dernière partie de cette thèse, des résultats sont présentés sur l'étude des propriétés physico-chimiques et optiques de semi-conducteurs poreux : le GaAs et l'InP poreux. L'effet de confinement quantique dans les cristallites de GaAs poreux a été confirmé après avoir caractérisé optiquement par Photoréflectivité (PR) et photoluminescence (PL) des échantillons de GaAs poreux