Three-dimensional femtosecond laser structuring has a growing interest because of its ease of implementation and the numerous possible applications in the domain of photonic components. Structures such as waveguides, diffraction gratings, optical memories or photonic crystals can be fabricated thanks to this technique. Its use with oxide glasses is promising because of several advantages; they are resistant to flux and ageing, their chemical composition can easily be changed to fit the well-defined requirements of an application. They can already be found in Raman amplifiers, optical fibers, fiber lasers, and other devices. This thesis is based on two axes. The first axis consists in characterizing the linear and nonlinear optical properties of bulk vitreous materials in order to optimize their composition with a particular application in view. Within this context, the nonlinear optical properties, their physical origins (electronic and nuclear) as well as their characteristic response times (from a few femtoseconds to a few hundreds of picoseconds) are described within the Born-Oppenheimer approximation. Fused silica and several sodium-borophosphate glasses containing different concentrations in niobium oxide have been studied. Results show that the nonlinear optical properties of fused silica are mainly from electronic origin, whereas in the sodium-borophosphate glasses, the contribution from nuclear origin becomes predominant when the concentration of niobium oxide exceeds 30%. The second axis is based on the structuring of materials. Three commercially available fused silica samples presenting different fabrication conditions (therefore distinct impurity levels) and irradiated with a near infrared femtosecond laser have been studied. The laser induced defects have been identified by means of several spectroscopic techniques. They show the formation of color centers as well as a densification inside the irradiated area. Their linear refractive index and nonlinear third-order susceptibility properties have been measured. Moreover, the structuring of fused silica at the subwavelength scale into "nanogratings" is observed and the form of birefringence induced by these structures is discussed. In addition to the fused silica samples, several oxide glasses presenting very distinct chemical compositions have been studied. A sodium-borophosphate glass containing niobium oxide exhibits micro-cracks and nano-crystallites following irradiation. A silicate glass with or without a silver component reveals fluorescent rings or "nanograting" structures. A zinc phosphate glass containing silver also presents fluorescent ring structures, with a size of the order of 80 nm, well below the diffraction limit. Pump-probe microscope techniques have been performed on this glass to investigate the laser-glass interaction. The absorption mechanism is determined to be four-photon absorption. The generated free electron density is ~ 1017 cm-3, which suggests the conclusion that an electron gas rather than a plasma is formed during the laser irradiation.

Understanding cell migration is a key step in unraveling many physiological phenomena and predicting several pathologies, such as cancer metastasis. In particular, confinement has been proven to be a key factor in the cellular migration strategy choice. As our insight in the field improves, new tools are needed in order to empower biologists’ analysis capabilities. In this framework, microfluidic devices have been used to engineer the mechanical and spatial stimuli and to investigate cellular migration response in a more controlled way. In this work, we will review the existing technologies employed in the realization of microfluidic cellular migration assays, namely the soft lithography of PDMS and hydrogels and femtosecond laser micromachining. We will give an overview of the state of the art of these devices, focusing on the different geometrical configurations that have been exploited to study specific aspects of cellular migration. Our scope is to highlight the advantages and possibilities given by each approach and to envisage the future developments in in vitro migration studies under spatial confinement in microfluidic devices.

Topological states in photonic systems are described by qualitative discrete quantum numbers and feature unique combinations of properties such as robustness to perturbations and dissipationless surface transport of energy and information. Due to the many easily accessible platforms in photonics, topological photonics is one of the spearheads of topological physics that has offered exciting possibilities for investigations of novel topological phenomena and numerous promising technological uses. This master thesis aims at investigating from a theoretical and experimental perspective the properties of topological states of interacting light modes in arrays of coupled waveguides. First, we present a review of recent advances in the recently emerged field of topological physics. Then we review recent work on lattice models that feature topological edge states, and subsequently, we identify the existence of robust corner states on the edge of honeycomb lattices. These states display, similarly to the corner states known in 1D SSH and 2D Kagome lattices, exponential localisation with naturally occurring total destructive interference. Additionally, the corner states share properties with the dynamic transport modes of photonic Floquet topological insulators. However, the origin of the corner localisation is different from the previously studied examples: instead of dimerised coupling strength, the asymmetric and dimerised number of neighbours in the direction of the corner generates the intensity gradient. Motivated by our numerical study, we outline an experimental realisation of the novel honeycomb corner states, by means of waveguide lattices written in glass. The waveguides are 3D written in the bulk of a glass sample, with the lattice pattern orthogonal to the main direction of propagation which acts as a time coordinate in the experiments. Femtosecond direct laser writing enables fabricating truly 3D waveguides. Our experimental preparations cover a study of the effects of fabrication parameters for the relevant structures. We discuss how the localisation and robustness properties of the honeycomb corner states would next be investigated in the prepared experimental setting. / Topologiska tillstånd i fotoniska system beskrivs av särskilda topologiska diskreta kvanttal och har unika kombinationer av egenskaper såsom robusthet mot fluktuationer och förlustfri yttransport av energi och information. Tack vare de många lättillgängliga plattformarna inom fotonik är topologisk fotonik en av spjutspetsarna inom topologisk fysik och har erbjudit unika möjligheter för undersökningar av nya topologiska fenomen och med många lovande tekniska användningsområden. Denna masteruppsats syftar till att undersöka, ur ett teoretiskt och experimentellt perspektiv, egenskaperna hos topologiska tillstånd av interagerande ljusmoder i gitter av kopplade vågledare. Först presenterar vi en översikt av de senaste framstegen inom det nyligen uppkomna området topologisk fysik. Sedan sammanfattar vi det senaste arbetet med gittermodeller som har topologiska kanttillstånd, och därefter identifierar vi förekomsten av robusta hörntillstånd på kanten av bikakegitter. Dessa tillstånd uppvisar, på samma sätt som hörntillstånden som är kända i 1D SSH- och 2D Kagome-gitter, hög kantlokalisering med naturligt förekommande total destruktiv interferens. Dessutom delar hörntillstånden egenskaper med de kända fotoniska Floquet-topologiska isolatorerna som uppvisar topologisk transport. Ursprunget till hörnlokaliseringen skiljer sig dock från de tidigare studerade exemplen: istället för en dimeriserad kopplingsstyrka genererar det asymmetriska och dimeriserade antalet grannar i hörnets riktning intensitetsgradienten. Med motivering i den numeriska studien inleder vi en experimentell realisering av de nya bikakehörntillstånden, med hjälp av vågledargitter skrivna i glas. Vågledarna är 3D-skrivna på insidan av ett glasprov, med gittermönstret ortogonalt mot huvudutbredningsriktningen som fungerar som en tidskoordinat i experimenten. Direkt laserskrivning med femtosekundlaser gör det möjligt att tillverka vågledare i tre dimensioner. Våra experimentella förberedelser omfattar en studie av effekterna av tillverkningsparametrar för de relevanta strukturerna. Vi diskuterar hur lokaliserings- och robusthetsegenskaperna för bikakehörntillstånden sedan skulle undersökas med den experimentella metoden.

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This dissertation elucidates a greater understanding of the vaporization and electrospray post-ionization mechanisms when using femtosecond laser pulses for desorption of surface molecules and electrospray ionization for capture and mass analysis of the gas phase ions. The internal energy deposition from nonresonant vaporization with femtosecond laser pulses was measured using dried and liquid samples of p-substituted benzylpyridinium ions and peptides. In the comparison of the experiments of using 800 nm and 1042 nm laser pulses, it was found that there are different vaporization mechanisms for dried and liquid samples. It was established that LEMS is a "soft" mass analysis technique as it resulted in comparable internal energy distributions to ESI-MS with one caveat; multiphoton excitation of dried samples results in extensive fragmentation at higher pulse energies. The quantitative aspects of the laser electrospray mass spectrometry (LEMS) technique were established using various multicomponent mixtures of small biomolecules. Experiments with LEMS resulted in similar quantitative characteristics to ESI-MS except that ESI-MS demonstrated a greater degree of ion suppression when using higher concentrations, particularly in the four-component mixture. The lack of ion suppression in the LEMS measurements was due to the ~1% neutral capture efficiency and most likely not a result of nonequilibrium partitioning. This was supported by the excess charge limit not being surpassed in the LEMS experiments and the quantitative analysis requiring the use of response factors. This dissertation also expanded upon the use of multivariate analysis for the classification of samples that were directly mass analyzed without any sample preparation using LEMS. A novel electrospray complexation mixture using cationic pairing agents, a lipid, and sodium acetate enabled the simultaneous detection of positive, neutral and negative charged features of inorganic-based explosive residues in a single experiment. This complexation mixture also enabled the detection of new features from an RDX-based propellant mixture. Principal component analysis (PCA) proved reliable for accurate classifications of the explosive mixtures. PCA was also used for accurate classification of eight phenotypes of Impatiens plant flower petals after mass analysis with LEMS. The PCA loading values were used to identify the key biomarkers in the classification. These important mass spectral features were identified as the biologically-relevant anthocyanins, which are phytochemicals that are responsible for the color of the flower petals. / Chemistry

The central objective of this work is developing convenient general procedures for controlling the formation and stabilization of nanoscale transition metal particles. Contemporary interest in developing alternative synthetic approaches for producing nanoparticles arises in large part from expanding applications of the nanomaterials in areas such as catalysis, electronics and medicine. This research focuses on advancing the existing nanoparticle synthetic routes by using a new class of polymer colloid materials as a chemical approach, and the laser irradiation of metal salt solution as a photo-chemical method to attain size and shape selectivity. Controlled synthesis of small metal nanoparticles with sizes ranging from 1 to 5nm is still a continuing challenge in nanomaterial synthesis. This research utilizes a new class of polymer colloid materials as nano-reactors and protective agents for controlling the formation of small transition metal nanoparticles. The polymer colloid particles were formed from cross-linking of dinegatively charged metal precursors with partially protonated poly dimethylaminoethylmethacrylate (PDMAEMA). Incorporation of [PtCl6]2- species into the colloidal particles prior to the chemical reduction was effectively employed as a new strategy for synthesis of unusually small platinum nanoparticles with narrow size distributions (1.12 ± 0.25nm). To explore the generality of this approach, in a series of proof-of-concept studies, this method was successfully employed for the synthesis of small palladium (1.4 ±0.2nm) and copper nanoparticles (1.5 ±0.6nm). The polymer colloid materials developed in this research are pH responsive, and are designed to self-assemble and/or disassemble by varying the levels of protonation of the polymer chains. This unique feature was used to tune the size of palladium nanoparticles in a small range from 1nm to 5nm. The procedure presented in this work is a new convenient room temperature route for synthesis of small nanoparticles, and its application can be extended to the formation of other transition metals and alloy nanoparticles. This research also focuses on developing new photo-chemical routes for controlling the size and shape of the nanoparticles through high-intensity ultra-fast laser irradiation of metal salt solution. One of the core objectives of this work is to explore the special capabilities of shaped laser pulses in formation of metal nanoparticles through irradiation of the solutions by using simultaneous spatial and temporal focusing (SSTF). Femtosecond laser irradiation has not yet been widely applied for nanoparticle synthesis, and offers new regimes of energy deposition for synthesis of nanomaterials. Photo-reduction of aqueous [AuCl4]- solution to the gold nanoparticles (AuNPs) has been applied as a model process for optimizing the experimental procedures, and evaluating the potential of shaped laser pulses in the synthesis of AuNPs. Systematic manipulation of the laser parameters and experimental conditions provided effective strategies to control the size of Au nanoparticles in strong laser fields. Varying the concentration of polyethylene glycol (PEG45) as a surfactant effectively tuned the size of AuNPs from 3.9 ±0.7nm to 11.0 ±2.4nm, and significantly increased the rate of Au(III) reduction during irradiation. Comparative studies revealed the capability of shaped laser pulses in the generation of smaller and more uniform AuNPs (5.8 ±1.1nm) relative to the other conventional laser irradiation methods (7.2 ±2.9nm). Furthermore, a new laser-assisted approach has been developed for selective formation of triangular Au nanoplates in the absence of any surfactant molecule. This method relies on rapid energy deposition by using shaped, ultra-intense laser pulses to generate Au seeds in aqueous [AuCl4]- solution, and the slow post-irradiation reduction of un-reacted [AuCl4]- species by using H2O2 as a mild reducing agent. Variation of the laser irradiation-time was found as an effective strategy to tune the morphology of Au nanomaterials from nanospheres to triangular nanoplates. The surfactant-free Au nanoplates produced in this research can be readily functionalized with a variety of target molecules or surfactants for desirable applications such as biomedicine. The concept of rapid laser processing followed by in situ chemical reduction can be expanded as a general methodology for high-yield production of nanomaterials, and provides a series of new laser dependent parameters for controlling the nanoparticle formation. / Chemistry

The higher-order modes (HOMs) of an optical fiber has been demonstrated as a new dimension to transmitting signals with the development of mode-division multiplexing (MDM) technique. This dissertation aims to explore the HOMs as an extra degree of freedom for device innovation. In particular, with femtosecond (FS) laser point-by-point (PbP) inscription technique which opens up a unique possibility to explore the HOMs for device innovation, we design, fabricate, and characterize novel-structured fiber Bragg gratings (FBGs) written in the step-index two-mode fibers. We also develop a numerical model for the PbP gratings which has the potential for inverse design problem. Chapter 2 begins with a general framework of MDM with adaptive wavefront shaping in few-mode fibers (FMFs) and multimode fibers (MMFs), followed by two examples in slightly more detail. The fabrication setup and an short overview of the FS laser system will also be covered. In Chapter 3, we show the design, fabrication, and characterization of off-axis Bragg gratings in a step-index two-mode fiber (TMF). Through measuring the transmission and reflection spectra along with the associated reflected mode intensity profiles under different input polarization, we experimentally investigate the off-axis TM-FBGs (FBGs in a TMF) with multiple characteristics reported for the first time to our best knowledge. To highlight, we report the laser-induced birefringence exhibits strong offset dependence, the reflectivity heavily depends on the offset and polarization, and particularly the mode pattern can be controlled solely through polarization. The design and characterization of cross-axis TM-FBGs are presented in Chapter 4. Specifically, these gratings show six primary reflection peaks, which are identified through mode-decomposition based on the intensity profiles through nonlinear optimization problem. We also show in this chapter the development of a numerical model for the general PbP gratings, implementation of this model into standard coupled-wave analysis shows reasonable agreement to the experimental findings. In Chapter 5, discussions and suggestions for future studies are given. / Doctor of Philosophy / The higher-order modes (HOMs) of an optical fiber has been demonstrated as a new space for signal transmission, in the ``mode space'' one can use the modes as distinct multiplexing channel and therefore increase the data capacity of a single fiber. This work aims to explore if the the higher-order modes can also add some extra degree of freedom for device innovation. In particular, we use femtosecond (FS) laser point-by-point (PbP) technique for device fabrication, since the structural change induced by this fabrication methods is highly localized, typically ranging from a few hundred nanometers to a few micrometers. Hence this particular fabrication technique offers a unique possibility of exploiting the HOMs for device innovation. In this work, we fabricate, and characterize fiber Bragg gratings (FBGs) with novel structural designs written within the step-index two-mode fibers, with multiple characteristics reported for the first time as far as we know. We also develop a numerical model for the PbP gratings which has the potential for inverse design problem.

Thesis (MSc)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: The demand for renewable energy sources has grown out of the humanity’s increasing need for electricity as well as depleting fossil fuel reserves. Organic-dye sensitised solar cells were developed as a green, cost-effective alternative to the market-dominating silicon solar cell technology. The field of photovoltaic devices and organic-DSSCs is interesting because we want to develop better, more efficient cells at lower costs using environmentally friendly materials. By studying the fundamental physics and chemistry processes occurring during and after the interaction of light with these devices, we create a window into the mechanism of photosynthesis. Our DSSCs were prepared by sensitisation of highly porous ZnO with different indoline dyes containing the same chromophore, but different alkyl chain lengths bonded to one of two carboxyl anchors as: DN91 (1 C) < DN216 (5 C) < DN285 (10 C). The role of the dye molecules is to absorb photons and donate electrons to the ZnO which acts as the charge acceptor, at the dye|ZnO interface. Through photoelectrochemical characterisation it was found that the structure of the dyes has an effect on the maximum current (JSC) produced by the cells: the shorter the alkyl chain, the higher the JSC. This macroscopic investigation was complimented by microscopic measurements in the form of transient absorption spectroscopy. This allows us to follow, in real time, the photoinduced oxidation of the dye and its regeneration occurring through desired and undesired pathways. It was found that the injection efficiencies of the dye molecules were directly responsible for the trend in the short circuit currents. / AFRIKAANSE OPSOMMING: Die aanvraag na die ontwikkeling van herwinbare energie bronne spruit voort uit die voorsienbare uitputting van fossiel brandstof bronne sowel as die groeiende behoefte om aan die mensdom se elektrisiteit behoeftes te voldoen. Kleurstof gesensitiseerde sonselle is ontwikkel as ’n groen, koste-effektiewe alternatief tot die silikon sonsel tegnologie wat die mark domineer. Die fotovoltaïse toestel veld, spesifiek organiese kleurstof gesensitiseerde sonselle is interessant omdat daar ruimte bestaan vir die ontwikkeling van beter meer effektiewe selle in terme van vervaardigings koste en prosesse wat omgewingsvriendelik is. Deur die fundamentele fisika en chemiese prosesse wat plaas vind tydens en na lig interaksie met hierdie selle te bestudeer gee dit insig oor die werkingsmeganisme van fotosintese. Ons kleurstof gesensitiseerde sonselle is voorberei deur sensitasie van hoogs poreuse ZnO met verskillende indolien kleurstowwe wat dieselfde kromofoor bevat wat met verskillende alkiel ketting lengtes verbind is aan een van twee karboksiel ankers as: DN91 (1 C) < DN216 (5 C) < DN285 (10 C). Die rol van die kleurstof molekules is om fotone te absorbeer en elektrone te doneer aan die ZnO wat as die lading akseptor dien by die kleurstof|ZnO intervlak. Deur fotoelektrochemiese karakterisasie is bevind dat die struktuur van die kleurstof ’n effek het op die maksimum stroom (JSC) wat die selle produseer: hoe korter die die akiel ketting, hoe hoër die JSC. Hierdie makroskopiese ondersoek is voltooi deur mikroskopiese metings in die vorm van tydopgelosde absorpsiespektroskopie. Dit laat ons toe om die fotogeinduseerde oksidasie asook regenerasie van die kleurstof te volg soos wat dit plaas vind deur gewenste sowel as ongewenste roetes. Dit is bevind dat die inspuitings effektiwiteit van die kleurstof molekules direk verantwoordelik is vir die waarneembare trajek in die kortsluitings stroom.