Les cristaux photoniques (CP) 3D sont des matériaux périodiques dont l’indice de réfraction varie périodiquement à l’échelle de la longueur d’onde. Cette propriété optique permet d’élaborer des composants optiques spécifiques comme des miroirs pour les lasers de puissance. Ces structures doivent présenter une meilleure tenue au flux laser (TFL) en régime sub-nanoseconde, comparés aux revêtements miroirs multidiélectriques actuels. Cette propriété est attendue car un unique matériau présentant une bonne TFL est utilisé pour leur élaboration, la silice. Cette étude présente donc le développement de cristaux photoniques colloïdaux 3D en utilisant la technique de Langmuir-Blodgett. Ces CP sont constitués de particules de silice avec une distribution en taille étroite, synthétisées par voie sol-gel. Différentes synthèses ont donc été développées et comparées afin d’obtenir les meilleures propriétés réfléchissantes. Une modélisation a aussi été effectuée en incluant des défauts dans une structure parfaite pour just ifier certains résultats expérimentaux. / Three-dimensional photonic crystals (PCs) are periodic materials with a modulated refractive index on a length scale close to the light wavelength. This optical property allows the preparation of specific optical components like highly reflective mirrors. Moreover, these structured materials might have a high laser-induced damage threshold (LIDT) in the sub-nanosecond range compared to multi-layered dielectric mirrors. This property is obtained because only one high LIDT material (silica) is used. In this work, we present the development of 3D PCs with narrow-sized colloidal silica particles, prepared by sol-gel process and deposited with Langmuir- Blodgett technique. Different syntheses routes have been investigated and compared regarding the optical properties of the PCs. A numerical model based on an ideal opal network including defect influence is used to explain these experimental results.

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This diploma thesis is focused on preparation of perovskite methylammonium lead bromide thin film layers and also thin film layers of its precursors, namely methylammonium bromide and lead(II) bromide, by spin-coating from the solution; and optical characterisation of the prepared thin film layers by UV-VIS spectroscopy and spectroscopical ellipsometry. Methylammonium bromide does not absorb in visible nor ultraviolet region, the maximum absorption of lead(II) bromide occurred in ultraviolet region, methylammonium lead bromide absorbs in visible region. Optical band gaps were determined by Tauc method to (3,5 ± 0,1) eV for lead(II) bromide and 2,15 eV, respectively 2,25 eV for perovskite. Refractive indices and extinction coefficients were determined by ellipsometry in range of wavelengths from 290 nm to 830 nm and their dependence with layer thickness was discussed. Ellipsometry model used in this thesis consist on Tauc-Lorentz oscillators for methylammonium bromide, methylammonium lead bromide and partially for lead(II) bromide, which another part is formed by New Amorphous oscillator.

This thesis deals with metal nanostructures and their use in detection of biomolecules. A protocol for stabilizing solutions of gold nanoparticles was developed for better usage in biological samples or biochemical processes, where different pH or salt concentrations can be used. A model of optical properties of the nanoparticles was presented and supported by spectroscopic experiments. A possible utilization of plasmonic nanostructures on surfaces for detection of biomolecules was also demonstrated.

The use of lasers for diagnosis and treatment in medical and cosmetic applications is increasing worldwide. Not all of these modalities are superficial and many require laser light to penetrate some distance into the tissue or skin to reach the treatment site. Human skin is highly scattering for light in the visible and near infrared wavelength regions, with a consequent reduction of the fluence rate. Melanin, which occurs in the epidermis of the skin, acts as an absorber in these wavelength regions and further reduces the fluence rate of light that penetrates through the epidermis to a treatment site. In vivo fluence rate measurements are not viable, but validated and calibrated computer models may play a role in predicting the fluence rate reaching the treatment site. A layered planar computer model to predict laser fluence rate at some depth into skin was developed in a commercial raytracing environment (ASAP). The model describes the properties of various skin layers and accounts for both the absorption and scattering taking place in the skin. The model was validated with optical measurements on skin-simulating phantoms in both reflectance and transmission configurations. It was shown that a planar epidermal/dermal interface is adequate for simulation purposes. In the near infrared wavelength region (676 nm), melanin (consisting of eumelanin and pheomelanin) is the major absorber of light in the epidermis. The epidermal absorption coefficient is one of the required input parameters for the computer model. The range of absorption coefficients expected for typical South African skin phototypes (ranging from photo-sensitive light skin, phototype I on the Fitzpatrick scale, to the photo-insensitive darker skin phototype V) was not available. Non-invasive diffuse reflectance spectroscopy measurements were done on 30 volunteers to establish the expected range of absorption coefficients. In the analysis it became apparent that the contributions of the eumelanin and pheomelanin must be accounted for separately, specifically for the Asian volunteers. This is a new concept that was introduced in the diffuse reflectance probe analysis. These absorption coefficient measurements were the first to be done on the expected range of skin phototypes for the South African population. Other authors dealing with diffuse reflectance probe analysis only account for the dominant eumelanin. Both the epidermal absorption coefficient and thickness are important in the prediction of the fluence rate loss. The computer model was used to evaluate the effect of the epidermal absorption coefficient (a parameter dictated by an individual’s skin phototype) and the epidermal thickness on the fluence rate loss through the skin. The epidermal absorption is strongly wavelength dependent with the higher absorption at the shorter wavelengths. In the computer model a longer wavelength of 676 nm (typical for a photodynamic treatment (PDT) of cancer) was used. For the darker skin phototypes (V) only about 30% of the initial laser fluence rate reached a depth of 200 ìm into the skin (just into the dermis). For the PDT application, results from the computer model indicated that treatment times need to be increased by as much as 50% for very dark skin phototypes when compared to that of very light phototypes. / Thesis (PhD)--University of Pretoria, 2012. / Physics / unrestricted

The first part of this dissertation deals with the application of a luminescence quenching method to measure diffusion and permeation coefficients of oxygen in polymers. Most luminescence oxygen sensors do not follow linearity of the Stern-Volmer (SV) equation due to heterogeneity of luminophore in the polymer matrix, thus the complexity of data analysis is increased. To circumvent this limitation, inverted fluorescence microscopy is utilized in this work to investigate the SV response of the sensors at the micron-scale. In these diffusion experiments, oxygen concentration is measured by luminescence changes in regions with high SV constants and good linearity. Thus, we avoid numerical complexity of combining nonlinear SV equation with a diffusion model. This technique allows us to measure oxygen diffusion properties in different type of polymers like transparent, opaque, free-standing polymers and polymers that cannot be cast into free standing films and polymer composites. In the second part of this thesis, we have explored the effect of Ag-Cu alloy nanoparticles on the emission intensity of luminophores at their close proximity. Alloy nanoparticles offer additional degrees of freedom for tuning their optical properties by altering atomic composition and atomic arrangement and thus can be an attractive option for manipulating signal of a wide range of luminophores. In this work, surface plasmon resonance spectrum of Ag-Cu alloy nanoparticles deposited by sputtering was easily tuned in wide wavelength range by varying one experimental condition- annealing temperature. Large metal enhanced luminescence for different luminophores viz Alexa Fluor 594 and Alexa Fluor 488 were achieved at the vicinity of Ag-Cu nanoparticles when maximum spectral overlap between SPR spectra of Ag-Cu nanoparticles and the emission and absorption spectra of the luminophores occur. We also studied the effect of composition of Ag-Cu nanoparticles synthesized by the polyol process on the luminescence of low quantum yield dye Cy3. In the third part of this thesis, quenching effect of Cu nanoparticles on CdSe/ZnS nanocrystal quantum dots has been explored. As Cu nanoparticles have comparable dielectric properties with gold nanoparticles, they are expected to show similar quenching effects. It was found that Cu is an efficient quencher of fluorescence from CdSe/ZnS quantum dots and the quenching effect is due to resonance energy transfer from quantum dots to Cu nanoparticles.

<p>Functional oxide-based thin films have attracted much attention owing to their broad applications in modern society. The multifunction tuning in oxide thin films is critical for obtaining enhanced properties. In this dissertation, four new nanocomposite thin film systems with highly textured growth have been fabricated by pulsed laser deposition technique. The functionalities including ferromagnetism, ferroelectricity, multiferroism, magnetoelectric coupling, low-field magnetoresistance, transmittance, optical bandgap and dielectric constants have been demonstrated. Besides, the tunability of the functionalities have been studied via different approaches.</p> <p>First, varies deposition frequencies have been used in vertically aligned nanocomposite BaTiO₃:YMnO₃ (BTO:YMO) and BaTiO₃:La_0.7Sr_0.3Mn₃(BTO:LSMO) thin films. In both systems, the strain coupling effect between the phases are affected by the density of grain boundaries. Increasing deposition frequency generates thinner columns in BTO:YMO thin films, which enhances the anisotropic ferromagnetic response in the thin films. In contrast, the columns in BTO:LSMO thin films become discontinuous as the deposition frequency increases, leading to the diminished anisotropic ferromagnetic response. Coupling with the ferroelectricity in BTO, the room temperature multiferroic properties have been obtained in these two systems.</p> <p> Second, the impact of the film composition has been demonstrated in La_0.7Ca_0.3MnO₃ (LCMO):CeO₂thin film system, which has an insulating CeO₂in ferromagnetic conducting LCMO matrix structure. As the atomic percentage of the CeO₂increases, enhanced low-field magnetoresistance and increased metal-to-insulator transition temperature are observed. The thin films also show enhanced anisotropic ferromagnetic response comparing with the pure LCMO film.</p> <p> Third, the transition metal element in Bi₃MoM_TO₉(M_T, transition metals of Mn, Fe, Co and Ni) thin films have been varied. The thin films have a multilayered structure with M_T-rich pillar-like domains embedded in Mo-rich matrix structure. The anisotropic magnetic easy axis and optical properties have been demonstrated. By the element variation, the optical bandgaps, dielectric constants as well as anisotropic ferromagnetic properties have been achieved. </p> <p> The studies in this dissertation demonstrate several examples of tuning the multifunctionalities in oxide-based nanocomposite thin films. These enhanced properties can broaden the applications of functional oxides for advanced nanoscale devices.</p><br>

Light is electromagnetic radiation that could be shown in a spectrum with a wide range of wavelengths. Blackbody radiation is a type of thermal radiation and is an important topic to explore due to it being an ideal body that materials’ properties are often described in comparison to it. Therefore, it helps in understanding how materials behave on the quantum level. One must understand its interaction with light spectrum and how electron excitation happens. Thus, concepts such as Planck’s law, energy quantization and band theory will be discussed to try to grasp of how light interacts with materials.

Les composés pérovskites halogénés AMX3 (A+ est un cation organique ou inorganique monovalent : Cs+, méthylammonium [CH3NH3]+ (MA) ; M2+ un cation métallique bivalent comme le Pb2+ et X un anion halogénure I-, Br- ou Cl-) possèdent des propriétés remarquables pour les absorbeurs des cellules photovoltaïques. La structure pérovskite offre la possibilité de moduler facilement les propriétés des matériaux en modifiant leur composition chimique : leur largeur de bande interdite peut être ajustée en variant la nature de l’halogène. Les travaux menés au sein de cette thèse portent sur l'élaboration et la caractérisation approfondie de matériaux pérovskites halogénés mixtes – c'est-à-dire avec un mélange d’ions sur les sites A, M ou X – de faibles dimensions tels que les couches minces et les nanocristaux.Un protocole de fabrication de cellules pérovskites de référence avec les absorbeurs CH3NH3PbI3 et CH3NH3PbI3-xClx et un rendement dépassant 10 % a été établi. Ceci a permis de fabriquer des couches minces pérovskites avec une épaisseur contrôlée et de manière reproductible sur différents substrats de TiO2 (compact, mésoporeux ou monocristallin). L’étude de ces couches par diffraction des rayons X au laboratoire et au synchrotron a mis en évidence une orientation préférentielle (001) des cristallites pour CH3NH3PbI3-xClx quel que soit le type de substrats de TiO2. En utilisant un substrat TiO2 monocristallin nous démontrons pour la première fois que le degré d’orientation et la taille des grains sont fortement augmentés (taux de couverture de surface 80%) par rapport aux substrats contenant du TiO2 mésoporeux ou une couche compacte polycristalline. La présence du chlore à l’interface TiO2–pérovskite et la faible rugosité du substrat sont des facteurs clés favorisant la croissance de cristallites orientés.Dans la deuxième partie de la thèse, l’influence de la substitution partielle du Pb2+ par des cations métalliques homovalents non toxiques (alcalino-terreux et métaux de transitions 3d) sur la structure et les propriétés optiques des nanocristaux pérovskite hybrides et inorganiques a été étudiées. La morphologie et la taille des nanocristaux hybrides MAPb1-xMxBr3 synthétisés par méthode de reprécipitation est largement impactée malgré une faible substitution (x : maximum 6% avec Mg2+). Au contraire dans les nanocristaux inorganiques CsPb1-xMxX3, synthétisés par injection à chaud, jusqu’à 16% du Pb2+ peut être remplacé par du Mg2+ ou du Sr2+ en conservant leur taille, forme, structure, propriétés d’absorption et de photoluminescence. Pour un taux de substitution plus élevé (une valeur maximale de 22% a été atteinte), la formation de la structure Cs4PbX6 est favorisée. / Metal halide perovskites AMX3 (A+ is an organic or inorganic cation: Cs+ methylammonium [CH3NH3]+ (MA); M2+ is a metallic cation such as Pb2+ and X a halide anion I-, Br- or Cl-) have remarkable properties as solar cell absorbers. In the perovskite structural framework the properties of the materials can be easily tailored by modifying their chemical composition. Changing for example the halide anion modulates their band gap. This thesis deals with the synthesis and the advanced characterisation of mixed halide perovskite materials – i.e. with mixed ions on the same site A, M or X – of low dimensions such as thin films and nanocrystals.A fabrication protocol was developed for reference solar cells with CH3NH3PbI3 and CH3NH3PbI3-xClx absorbers yielding a power conversion efficiency over 10%. The perovskite thin films could be fabricated with a controlled thickness and a high reproducibility on different TiO2 substrates (compact, mesoporous or monocrystalline). The study of these thin films by laboratory and synchrotron X-ray diffraction showed that the CH3NH3PbI3-xClx crystallites exhibit a preferential (001) orientation on any kind of TiO2 substrate. By using monocristalline TiO2 substrates we showed for the first time that the degree of orientation and the grain size increased considerably (the surface coverage was determined to be 80%) compared to mesoporous and compact polycrystalline TiO2 substrates. The presence of chlorine at the TiO2–perovskite interface and the low surface roughness of the substrate are key factors, which promote the growth of highly oriented crystallites.In the second part of the thesis, the influence of the partial substitution of lead with non-toxic homovalent metal cations (alcaline earth, 3d transition metals) on the structural and optical properties of hybrid and inorganic perovskite nanocrystals was studied. The morphology and the size of MAPb1-xMxBr3 hybrid nanocrystals synthesised by reprecipitation is clearly affected despite the low substitution (x: maximum 6% with Mg2+). Conversely, in CsPb1-xMxX3 inorganic nanocrystals synthesised by hot injection, up to 16% of Pb2+ could be replaced by Mg2+ or Sr2+, while keeping their size, shape, structure, absorption and photoluminescence properties. With a higher substitution ratio (up to 22% was achieved), the formation of the Cs4PbX6 structure is favoured.

A Nephelometry camera (NephCam) and Humidity Controlled Cavity Ring-Down Transmissometer (HC-CRDT) were developed for the determination of aerosol optical properties. The NephCams use a reciprocal geometry relative to an integrating nephelometer; a diode laser illuminates a scattering volume orthogonal to a charge coupled device (CCD). The use of a CCD allows for measurement of aerosol scattering in 2 dimensions; scattering coefficients and size information can be extracted. The NephCam's optics were characterized during a set of imaging experiments to optimize the images collected by the camera. An aperture setting of 1.6 was chosen because it allowed for the most light intensity to reach the CCD - albeit with significant vignetting - and also had a constant modular transfer function (MTF) across the image; approximately 0.3. While this MTF value is approaching the minimum usable MTF of 0.2, other aperture settings did not exhibit constant MTF. While the effects of vignetting can be corrected in image post processing, the effects of non-constant MTF cannot. An optical response model was constructed to simulate images collected by the NephCams as a function of particle type and size. Good agreement between modeled and measured images was observed after the effects of contrast on image shape were considered. The image shapes generated by the model also pointed towards the use of polynomial calibration for particle sizes less than 400 nm as a result of multiple charge-to-size effects present from the sizing mechanism of the differential mobility analyzer. Initial calibration of the NephCams using size-selected dry Ammonium sulfate (AS) showed that calibration slopes are a function of particle size which is also in agreement with the model. Calibration slopes decreased as particle size increased to 400 nm; after 400 nm calibration slope oscillated around a common value. This effect is directly related to the forward shift of scattered intensity as particles grow in size and the collection efficiency of the NephCam as particle size increases. The single scattering albedo (SSA) of Nigrosin was calculated using the NephCam; extinction was measured by the HC-CRDT. Good agreement between the SSA and size was noticed for larger particle sizes; particles smaller than 200 nm in diameter over-measured the SSA of Nigrosin because of the multiple charge-to-size effect. In this size regime, light scattering by particles increases much more quickly than absorption; the presence of larger particles causes scattering to be artificially high. The HC-CRDT is a 4 channel, 3 wavelength instrument capable of measuring the extinction coefficients of aerosols at high (> 80%), low (< 10%) and ambient relative humidity. Extinction coefficients as a function of RH were determined for AS, NaNO3, NaCl, and Nigrosin; these particles represent surrogates of the strongly scattering ionic salts and black carbon, respectively. A model was developed to calculate the changes in refractive index and extinction coefficients of these water soluble particles as a function of RH; these particle types were chosen because core-shell morphologies could be avoided. Volume mixing, Maxwell-Garnett and partial molar refraction mixing rules were used to calculate effective refractive indices as a function of water uptake. Particle growth was calculated based upon the Kelvin equation. Measured and modeled results of f(RH) - relative change in extinction between high or ambient RH and dry RH - agree well for all particle types except Nigrosin. This disagreement is thought to stem directly from an incomplete parameter set for Nigrosin; growth parameters were assumed to be identical to NaNO3, density assumed to be 1 g/mL and molecular weight 202 g/mole, which may not be true in reality (different suppliers of Nigrosin quote different molecular weights). The NephCam was not used during these experiments, so the addition of a scattering measurement to better characterize the growth by Nigrosin is necessary. The f(RH) data for NaNO3 showed excellent agreement between measured and modeled data; however particle size information collected by an SMPS does not agree with the theory. This stems from the fact that NaNO3 does not show prompt deliquescence upon drying; instead an amorphous solid forms which exhibits a kinetically limited loss of water.