While silicon has long been utilized for its electronic properties, its use as an optical material has largely been limited due to the poor efficiency of interband transitions. However, discovery of visible photoluminescence (PL) from nanocrystalline silicon in 1990 triggered many ensuing research efforts to optimize PL from nanocrystalline silicon for optical applications. Currently, use of photoluminescent silicon nanoparticles (Si NPs) is commercially limited by: 1) the instability of the energy and intensity of the PL, and 2) the low quantum yield of interband PL from Si NPs. Herein, red-emitting, hydrogen-passivated silicon nanoparticles (H-Si NPs) were synthesized by thermally-induced disproportionation of a HSiCl3-derived (HSiO1.5)n polymer. The H-Si NPs produced by this method were then subjected to various chemical and physical environments to assess the long-term stability of the optical properties as a function of changing surface composition. This dissertation is intended to elucidate correlations between the reported PL instability and the observed changes in the Si NP surface chemistry over time and as a function of environment. First, the stability of the H-Si NP surface at slightly elevated temperatures towards reactivity with a simple alkane was probed. The H-Si NPs were observed by FT-IR spectroscopy to undergo partial hydrosilylation upon heating in refluxing hexane, in addition to varying degrees of surface oxidation. The unexpected reactivity of the Si surface in n-hexane supports the unstable nature of the H-Si NP surface, and furthermore implicates the presence of highly-reactive Si radicals on the surfaces of the Si NPs. We propose that reaction of alkene impurities with the Si surface radicals is largely responsible for the observed surface alkylation. However, we also present an alternate mechanism by which Si surface radicals could react with alkanes to result in alkylation of the surface. Next, the energy and intensity stability of the interband PL from H-Si NPs in the presence of a radical trap was probed. Upon addition of (2,2,6,6,-tetramethyl-piperidin-1-yl)oxyl (TEMPO), the energy and intensity of the interband transition was observed to change over time, dependent on the reaction conditions. First, when the reaction occurred at 4ºC with minimal light exposure, the interband transition exhibited a gradual hypsochromic shift to between 595 nm and 655 nm, versus the λmax of the original low energy emission peak at 700 nm, depending on the amount of TEMPO in the sample. Second, when the reaction proceeded at room temperature with frequent exposure to 360 nm irradiation, the original interband transition at 660 nm was quenched while a new peak at 575 nm developed. Based on all the data collected and analyzed, we assign the 595 -- 655 nm transition as due to interband exciton recombination from Si NPs with reduced diameters relative to the original Si NPs. We furthermore assign the 575 nm transition as due to an oxide-related defect state resulting from rapid oxidation of photo-excited Si NPs.

Nous avons étudié par spectroscopie de Résonance Paramagnétique Électronique (RPE), par simulation de spectre RPE, par spectroscopie Raman et par photoluminescence les ions Ti3+ formés par irradiation aux β de 3,37 x 10^5 à 1,68 x 10^9 Gy dans les verres SiO2 - Na2O - TiO2 et SiO2 - Al2O3 - B2O3 - Na2O - TiO2. Nous montrons que ces ions existent dans les verres silicatés dans trois sites différents correspondant à trois environnements différents : [VI]Ti3+, [V]Ti3+ sous forme de pyramide à base carrée et peut être sous forme de bi-pyramide. Il existe de même trois sites des ions Ti3+ dans les verres alumino-borosilicatés et le site des ions [VI]Ti3+ est commun aux deux classes de verres. L'étude de l'évolution des proportions d'ions Ti3+ dans chacun des sites ainsi que l'étude des paramètres RPE des sites montre que leur existence est déterminée par la dose intégrée et la valeur du rapport [Na]/[Ti] que nous redéfinissons dans le cas des verres alumino-borosilicatés. Enfin, sous une excitation à 266 nm nous observons à température ambiante une bande d'émission à 500 nm attribuée aux ions Ti4+. Sous une excitation à 532 nm, nous observons une bande d'émission à 590 nm avec des temps de vie courts d'une centaine de ns que nous attribuons soit aux ions Ti3+ soit à des défauts formés près des ions Ti4+. Dans l'ensemble, cette étude montre donc qu'il est possible de contrôler par la chimie et la dose intégrée l'environnement des ions Ti3+ et donc les propriétés d'émission de cet ion dans un verre.

Graduation date: 1996

This thesis presents results of time-resolved photoluminescence experiments conducted on several different self-assembled InGaAs/GaAs and InAs/GaAs semiconductor quantum dot (QD) structures. Depending on the application in mind, different structural, electronic or optical properties have a different weight of importance. Fast carrier capture and relaxation is critical for QD based lasers, for example. In this thesis, the influence of surplus carriers, introduced through modulation-doping, is studied. It is shown that carrier capture is essentially unaffected whereas the intradot relaxation mechanisms, at least at low carrier concentrations, are fundamentally different. The phonon mediated cascade relaxation found in the undoped reference sample is replaced by efficient scattering with the built-in carriers in the case of the doped structures. Moreover, spin relaxation also depends on presence of extra carriers. During energy relaxation via carrier-carrier scattering, the spin polarization is preserved whereas in the undoped sample the strong interaction of relaxing carriers with LO phonons causes spin relaxation. The decay of the ground state spin polarization proceeds at the same rate for doped and undoped structures and is shown to be caused by acoustic phonons, even up to 300 K. While optimizing QD growth for specific applications, it is imperative to evaluate the influence of nonradiative recombination, which is most often detrimental. While misfit dislocations, deliberately introduced in the substrate, lead to the formation of laterally ordered, uniform dots, these samples are found to suffer from strong nonradiative recombination. Structures with different barrier thicknesses and numerical simulations indicate defects in the vicinity of the QDs as main origin of fast carrier trapping. On the other hand, it is shown that direct dot doping, compared to barrier doping or undoped structures, causes only minor degradation of the optical properties. Directly doped dots even exhibit a significantly weaker photoluminescence quenching with temperature, making them prospective for devices operating at room temperature. Finally, the superior proton radiation hardness of QD structures compared to quantum wells is demonstrated, which is due to the three-dimensional confinement. The increase of photoluminescence intensity at low to moderate doses is interpreted as an enhanced carrier transfer into the dots via the defects introduced into the material by the protons. / QC 20100920

Ce travail de thèse présente les caractéristiques optiques et électriques de dopants dans des couches de CdHgTe, CdZnTe et CdS. Ces 3 matériaux II-VI ont pour point commun d'être utilisés dans des dispositifs de détection, que ce soit la détection de lumière infrarouge pour les couches de CdHgTe et CdZnTe ou la détection visible comme c'est le cas pour le CdS. La caractérisation optique de ces couches de matériaux II-VI a été réalisée par la technique de photoluminescence et corrélée à des mesures électriques effectuées par effet Hall en température. Dans un premier temps, une étude du dopage intrinsèque par les lacunes de mercure et du dopage extrinsèque par incorporation d'arsenic de l'alliage CdHgTe, couche active des détecteurs IR a été réalisée. Pour cela, des mesures optiques par photoluminescence (sur un banc mis en place au laboratoire pendant la 1ere année de thèse permettant de travailler depuis les basses températures jusqu'à l'ambiante entre 1µm et 12 µm dans l'IR) sur des couches de CdHgTe réalisées par épitaxie en phase liquide (EPL) de différentes compositions en Cd ont été effectuées. La corrélation de ces mesures optiques avec des mesures électriques par effet Hall en température a permis d'identifier les énergies d'activation des 2 niveaux de la lacune de mercure ainsi que de démontrer le phénomène de U-négativité de la lacune de mercure dans le CdHgTe. De plus, la comparaison de spectres de PL d'échantillons dopés arsenic pendant la croissance par épitaxie par jets moléculaires (EJM) avec des mesures disponibles réalisées par absorption de rayons X (EXAFS) a permis d'observer des transitions optiques associées aux différents complexes arsenic formés avant et après le recuit d'activation. Par ailleurs, un travail de modélisation du phénomène de désordre d'alliage dans le CdHgTe a été réalisé. Plus précisément, un modèle basé sur une statistique gaussienne associée aux fluctuations d'alliage autour d'un gap moyen et une statistique de Boltzman a été développé pour ajuster dans un premier temps des spectres d'absorption puis pour ajuster les spectres de photoluminescence. Ce modèle nous a permis d'ajuster étroitement les spectres de photoluminescence et d'absorption, tout en prenant en compte intrinsèquement le désordre d'alliage du matériau. Nous avons ainsi constaté que l'ajustement des spectres par des fonctions gaussiennes comme il est réalisé communément dans la littérature permet de trouver les bons écarts entre les pics d'émission et donc les bonnes énergies d'ionisation.. Dans un deuxième temps, toujours dans le cas de la détection infrarouge, le travail a porté sur l'étude du substrat CdZnTe utilisé pour l'épitaxie du CdHgTe. Des comparaisons des spectres de PL avec les paramètres de croissance ont été effectuées. Plus particulièrement, une étude sur une zone spécifique de certains échantillons présentant une absorption du rayonnement IR a été réalisée afin d'en comprendre l'origine. Enfin, nous nous sommes intéressés à la couche de CdS, matériau II-VI dopé intrinsèquement (type n) utilisé comme fenêtre transparente et formant la jonction p-n avec le CdTe dans les cellules solaires, détecteurs de lumière visible. Dans cette partie, nous avons chercher à étudier l'influence des différentes méthodes de dépôts, sublimation ou bain chimique de la couche de CdS sur un substrat de verre, en comparant les spectres d'émission de photoluminescence obtenus ainsi que les types de traitements thermiques effectués après dépôts. Ces mesures ont été corrélées avec le rendement des cellules solaires finales.

Optical amplifiers are highly sought-after in optical communications to power boost light signals carrying information. Rare Earth doped glasses have been the medium of choice for optical amplification. It is, therefore, essential to understand the interaction of light with potential host glasses for rare-earths before they could be proposed as suitable candidates. In this research, we have optically characterized three different rare earth doped bulk glasses. The glass samples investigated were Neodymium doped Gallium Lanthanum Sulfide (GLS:Nd), Erbium doped Germanium Gallium Sulfide (GeGaS:Er) and Erbium doped Fluorochlorozirconate (FCZ:Er). The transmission spectra, T(λ), was used in identifying the absorption transitions of rare earth ions from the ground level to the various excited levels and in obtaining the optical absorption coefficient, α(λ). This in turn was used in determining the Judd-Ofelt parameters, which were then used in obtaining radiative lifetimes of the energy levels of interest. Photoluminescence emission bands were also identified and their shapes were investigated. Finally, a comparison of the Judd-Ofelt lifetime with the experimental decay time was also done. From which, the major decay mechanism of the rare earth ions from the energy level under investigation was concluded.

A new form of antimicrobial surface was developed, which relies on an optical mechanism rather than chemical inactivation of microorganisms. Through the photoluminescence process of upconversion, low energy photons can be amplified into higher energy photons, and in this case, phosphors capable of converting visible light into germicidal UVC radiation were synthesized. Host crystals were doped with a praseodymium activator ion and shown to emit UVC photons upon excitation by blue or violet light. Surface coatings were prepared and proof-of-concept experiments demonstrated that, under exposure to a household fluorescent lamp, sufficient UVC radiation was emitted from the surfaces to achieve observable inactivation of surface bacterial spores and inhibition of biofilm growth. Material engineering was conducted to achieve higher optical conversion efficiency, wherein lithium codoping and development of alternative oxyfluoride host crystals were found to significantly improve upconversion emission. Implications of polychromatic excitation were investigated by conducting photoluminescence spectroscopy under combined laser beam excitation, while the effects of other application parameters are also discussed. These findings show that upconversion-based antimicrobial materials have strong potential for offering sustainable and effective technology for the prevention of diseases.

Microbeam Radiation Therapy (MRT) is an experimental form of radiation treatment which has the potential to improve the treatment of many types of cancer. In MRT, the radiation is applied as a grid by passing the collimated X-ray beam from a synchrotron through a microplane collimator, which is a stack of parallel plates of two materials with dramatically different X-ray transparencies. The peak-to-valley dose ratio (PVDR) is the difference between the dose in the microbeams and the dose delivered between the beams. It is the PVDR that is of biological importance in MRT. Therefore a dosimeter for MRT requires a combination of a large dynamic range for dose response into the kilo-Gray regime, and high spatial resolution on the micron scale. This project characterizes fluorophosphate glasses doped with trivalent samarium ions as a potential valency conversion dosimeter for MRT using the conversion of Sm3+→Sm2+ to measure the delivered dose. Samples irradiated at the Canadian Light Source synchrotron showed X-ray induced conversion that could be optically characterized by changes in the photoluminescence emission spectra to obtain irradiation dose. The conversion efficiency depends almost linearly on the irradiation dose up to 150 Gy and saturates at doses exceeding 1500 Gy. The conversion shows a strong correlation with an observed increase in absorbance of the glass in the range of 200-750 nm. The absorbance increases with X-ray dose and is related to the formation of phosphorous-oxygen hole centers (POHC) and POn electron centers. The presence of these defects within the irradiated glass was determined by examination of the induced optical absorbance and electron paramagnetic resonance (EPR) spectra. The formation of these hole centers along with the conversion of Sm3+→Sm2+ under X-ray irradiation suggests that the X-rays cause the formation of electron-hole pairs in the glass. The electrons are then primarily captured by the Sm3+ ions, becoming Sm2+ ions, with some of the electrons being captured by POn electron centers. The holes are captured by the POHCs. This process can be represented chemically as Sm3+ + e-→ Sm2+ and PO + h+→POHC. The stability of the Sm conversion under illumination was examined using photoluminescence spectra and the stability of the X-ray induced defects was examined via the induced optical absorbance and EPR spectra.

Optical amplifiers are highly sought-after in optical communications to power boost light signals carrying information. Rare Earth doped glasses have been the medium of choice for optical amplification. It is, therefore, essential to understand the interaction of light with potential host glasses for rare-earths before they could be proposed as suitable candidates. In this research, we have optically characterized three different rare earth doped bulk glasses. The glass samples investigated were Neodymium doped Gallium Lanthanum Sulfide (GLS:Nd), Erbium doped Germanium Gallium Sulfide (GeGaS:Er) and Erbium doped Fluorochlorozirconate (FCZ:Er). The transmission spectra, T(λ), was used in identifying the absorption transitions of rare earth ions from the ground level to the various excited levels and in obtaining the optical absorption coefficient, α(λ). This in turn was used in determining the Judd-Ofelt parameters, which were then used in obtaining radiative lifetimes of the energy levels of interest. Photoluminescence emission bands were also identified and their shapes were investigated. Finally, a comparison of the Judd-Ofelt lifetime with the experimental decay time was also done. From which, the major decay mechanism of the rare earth ions from the energy level under investigation was concluded.

The experiment divided into two parts. One is silicon solar cell process. The other is InGaN solar cell process. Borosilicafilm solution spin onto the n-type silicon (111) substrate and spread through the high-temperature furnace tube to form a p-n junction silicon solar cell. Then, evaporate top and rear contact by electron beam evaporation system. InGaN p-i-n structure solar cell grows on sapphire substrate by plasma-assisted molecular beam epitaxy system (PA-MBE) and its process is by repeated photolithography, inductive coupled plasma etching and wet etching. In the device fabrication process, the first is defining the sample size(mesa). Second, etched to the n-type GaN layer, and then coated metal as electrode. Finally, we get the device. In the measurement, the measurement of I-V curve of samples in the light by solar simulator of AM1.5 G light source observe open circuit voltage, short circuit current, fill factor, and efficiency. In addition, we measure the external quantum efficiency of the samples by IPCE and observe the photoelectric conversion efficiency of samples at different wavelength. Observed the sample quality and the indium composition of InGaN layer by XRD. We observe the InGaN band gap shift by variable-temperature photoluminescence spectra.