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<p>This thesis presents investigations on ultrafast laser irradiation of silicon towards the goal of hybridizing ultrafast laser processing and conventional semiconductor fabrication techniques to improve device applications. The fundamental sub-threshold damage accumulation mechanisms for potential defect engineering applications were studied through the use of positron annihilation spectroscopy, in situ sample heating during laser irradiation, varying the laser repetition rate, and samples implanted with various ion species at different conditions. Positron annihilation spectroscopy results suggest an increase in the divacancy density at the surface region of silicon following near- and slightly sub-threshold ultrafast laser irradiations. Laser irradiations at increasing sample temperature up to 600°C show a general decreasing trend of single-shot thresholds, and an increase in the suppression of sub-threshold damage accumulation. There is also a temperature dependence on the surface morphology resulting from ultrafast laser irradiation. Ion implantation modified the ablation threshold fluence, and a dependence on the ion implantation conditions was observed. Surface microstructuring of silicon was shown to improve absorption of light with a sub-bandgap wavelength of 1550 nm. An initial attempt with sulfur implantation did not exhibit further improvement in the optical absorption, and first attempts in device fabrication did not provide photoresponsivity at sub-bandgap wavelengths. Ultrafast laser irradiation of SiO₂-on-Si structures yielded different modification thresholds for different thicknesses of the oxide layer. Surface morphologies obtained in the irradiation of these structures can affect potential applications. Selected studies of ultrafast laser irradiation of GaP, metal-SiO₂-Si structures, quartz, diamond, and porcine bone demonstrated similarities in ablation behavior and morphologies, and the potential for a broad range of applications. The results in combination with the proposed future work in this thesis can contribute to potential device applications while providing valuable insights into the ultrafast laser ablation mechanisms.</p> / Doctor of Philosophy (PhD)

Femtosecond laser filamentation in gaseous media is a new source of broadband, ultrashort radiation that has the potential for application to many fields of research. In this dissertation filamentation is studied with a view to understanding the underlying physics governing the formation and propagation dynamics of filamentation, as well as to developing a method for vibrational spectroscopy based on the filament-induced impulsive vibrational excitation of molecules in the filamentation region. In pursuit of a better understanding of the underlying physical processes driving filamentation, the development of a new method for characterizing high intensity ultrashort laser pulses is presented, wherein two laser beams generate a transient grating in a noble gas, causing the pulse undergoing filamentation to diffract from the grating. Measuring the spectrum as a function of time delay between the filament and probe beams generates a spectrogram that can be inverted to recover the spectral and temporal phase and amplitude of the filamentary pulse. This technique enables measurement of the filamentary pulse in its native environment, offering a window into the pulse dynamics as a function of propagation distance. The intrinsic pulse shortening observed during filamentation leads to the impulsive excitation of molecular vibrations, which can be used to understand the dynamics of filamentation as well. Combined measurements of the longitudinally-resolved filament Raman spectrum, power spectrum, and fluorescence intensity confirm the propagation dynamics inferred from pulse measurements and show that filamentation provides a viable route to impulsive vibrational spectroscopy at remote distances from the laser source. The technique is applied to thermometry in air and in flames, and an analytical expression is derived to describe the short-time dynamics of the rovibrational wave-packet dispersion experienced by diatomic molecules in the wave of the filament. It is found that no energy is initially partitioned into the distribution of rovibrational states during the filamentation process. Filament-assisted impulsive stimulated Raman spectroscopy of more complex systems is also performed, showing that filament-assisted vibrational measurements can be used as an analytical tool for gas phase measurements and has potential for use as a method for standoff detection. Finally, a study of the nonlinear optical mechanisms driving the filamentation process is conducted using spectrally-resolved pump-probe measurements of the transient birefringence of air. Comparison to two proposed theories shows that a newly described effect, ionization grating-induced birefringence, is largely responsible for saturation and sign inversion of the birefringence at 400 nm and 800 nm, while the magnitude of contributions described by a competing theory that relies on negative terms in the power series expansion of the bound electron response remain undetermined. / Chemistry

No doubt, water is the most important liquid on the planet. In addition to the obligatory need for water in life, water is widely used in diverse applications. In most applications if not all, water is interfaced with different materials, at different phases depending on the application. This unique value of water originates from its chemical structure, which is based on hydrogen bonding. Although these chemical bonding in bulk liquid and vapor water have extensively been investigated, in interfacial water are not yet fully understood. This thesis presents an investigation of ultrafast vibrational dynamics of hydrogen bonding in interfacial water. In a first chapter, the experimental technique and tools needed for the study of interfacial vibrational dynamics are exposed. In the first part of a second chapter, vibrational coherence dynamics of free OH stretch modes at the alumina/water interface are investigated. And in the second part, vibrational coherence dynamics of hydrogen bonded OH stretch modes at the calcium fluoride/water interface are investigated. To understand the dynamics of vibrational energy flow within an interfacial network of hydrogen bonding, the investigation of vibrational coupling dynamics at the calcium fluoride/water interface takes place in a third chapter. Unlike what has already been reported in this topic, in our work, the vibrational energy will be initially deposited at the second vibrational excited state, through an overtone transition. / Chemistry

This dissertation expounds growing insight of the electrospray droplet ionization mechanism following ablation of dried hydrophobic and hydrophilic molecules using femtosecond laser pulses and mass analysis of the gas phase ions. Both hydrophobic and hydrophilic molecules were laser vaporized into an electrospray solvent opposite in polarity revealing appreciable ion intensity for all samples in contrast to ESI-MS and DESI measurements were solubility of the analyte in the spray solvent is a prerequisite. Quantitative analysis of equimolar protein solutions was established using LEMS reporting over three decades of quantitave response with little evidence of ion suppression. In contrast, ESI-MS measurements of similar equimolar protein solutions revealed severe ion suppression eliminating ion current from one of the protein analytes. Finally, the nature of an analyte following nonresonant laser vaporization has been the subject of debate. Aqueous trypsin was laser vaporized into an electrospray solvent containing either buffer or acid with substrate. LEMS measurements using buffer revealed enzyme-substrate intermediate charge states and continued enzymatic activity while the lack of enzyme-substrate intermediates and stymied enzymatic activity observed using acid suggests nonresonant laser vaporization preserves solution phase structure. This dissertation also extends considerably the use of LEMS for identification and characterization of energetic materials in their pre- and post-blast forms without sample preparation. The use of mulivarate analysis for the classification of large sample sets was also demonstrated showing high fidelity assignment of commercial formulations to their manufacturer. Five unburnt smokeless powders investigated using LEMS revealed unique combinations of organic molecules such as stabilizers and plasticizers using a simple electrospray solvent. Principal component analysis (PCA) provided exact classification of the mass spectra with respect to the manufacturer of the ordinance. LEMS measurements were then obtained from five commercial gunshot residue samples, or post-blast smokeless powder, revealing trace amounts of organics such as the stabilizers and large quantities of inorganic barium originating from the primer. Principal component analysis (PCA) again provided exact classification of the gunshot residue mass spectra with respect to the manufacturer of the ordinance. The use of a common transition metal complexation agent enabled full characterization of eight gunshot residue samples to include the heavy metals contained in the primer and the organics such as the stabilizers and plasticizers without any sample preparation or pre-concentration procedures. Principal component analysis (PCA) again provided high fidelity classification of the gunshot residue mass spectra with respect to the manufacturer of the ordinance after mass analysis with LEMS. Finally, highly energetic formulations such as composition 4 (C-4) and detonation cord subjected to nonresonant femtosecond laser vaporization enabled full characterization of these complex compositions identifying binders, stabilizers, the explosive ingredient and age-related decomposition derivative signature molecules with appreciable ion current detected using both positive and negative ion modes. / Chemistry

High-order harmonic generation (HHG), a non-perturbative nonlinear light-matter interaction resulting in coherent emission of high-frequency light, has demonstrated promise as an optical probe of carrier dynamics, structural symmetries, and other properties of solids. HHG from bulk solids in transmission geometry, however, is influenced by nonlinear propagation of the driving laser, which leads to spectral skewing and temporal phase variations in the harmonic emission. These effects obscure the microscopic underlying physics, making HHG-based spectroscopy of bulk solids difficult to interpret. HHG in few-to mono-layer materials, however, avoids strong nonlinear propagation effects, and can provide novel material properties for HHG studies. In this work, I compare HHG driven by femtosecond mid-infrared laser pulses in bulk and thin film solids. First, HHG generated from epitaxial ZnO thin films grown using different preparations is compared with HHG from bulk ZnO. I identify spectral signatures that result from nonlinear propagation in bulk samples, while thin films generally yield clean harmonic spectra with features that depend on the crystal growth and preparation. Specifically, I find that as-grown plasma ALD (atomic layer deposition) samples yield monocrystalline polar films, which is modified by annealing. The dependence of the harmonic yield on thickness of the nano-meter scale films was also experimentally measured and found to agree with simulations which incorporated nonlinear conductivity and linear propagation effects. Next, I examine the carrier envelope phase (CEP) dependence of HHG from bulk and thin-film ZnO. I observed a stronger-than-expected sensitivity of the HHG from bulk ZnO to CEP, which results from nonlinear self-compression of the pulse to single-cycle durations. Finally, experimental studies of HHG from novel van der Waals crystals are presented. Together, these results suggest novel frontiers for HHG from few-layer materials.

Thesis (MSc)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: Ultrafast electron diffraction is a powerful method to study atomic movement in crystals on sub-picosecond timescales. This thesis consists of three parts. In part one the ultrafast electron diffraction machine is described, followed by improvements that were made and techniques that were developed in order to bring the system to state of the art level and enable the acquisition of suffcient data to obtain information on the structural dynamics in crystals. The second part contains a description of the sample which was studied in our fi rst time-resolved measurements, the transition-metal dichalcogenide 4Hb-TaSe2. This particular crystal is an example of a strongly coupled electronic system which develops a charge density wave (CDW) accompanied by a periodic lattice distortion (PLD). An overview of the formation of electron diffraction patterns and what can be learned from them are also given, followed by the results of the ultrafast electron diffraction experiments done with 4Hb-TaSe2. Part three describes an alternative source to study dynamics in crystalline samples, namely laser plasma-based ultrafast X-ray diffraction. The ultrafast electron diffraction group functions as a unit, but my tasks ranged from sample preparation and characterisation of the electron beam to the setting up and execution of experiments. I was involved in analysing the data and contributed small parts to the data analysis software. / AFRIKAANSE OPSOMMING: Ultravinnige elektron diffraksie is a metode om die beweging van atome in kristalle op sub-pikosekonde tydskale te bestudeer. Hierdie tesis bestaan uit drie dele. In deel een van die tesis word die ultravinnige elektron diffraksie masjien beskryf, gevolg deur verbeteringe wat aangebring is en tegnieke wat ontwikkel is om die sisteem tot op 'n wêreldklas vlak te bring waar die insameling van genoegsame data om inligting oor die strukturele dinamika in kristalle te bekom, moontlik is. Die tweede deel bevat 'n beskrywing van die monster wat in ons eerste tydopgeloste eksperimente gebruik is, naamlik die oorgangsmetaaldichalkogenied 4Hb-TaSe2. Hierdie kristal is 'n voorbeeld van 'n sterk gekoppelde elektroniese sisteem wat 'n ladingsdigtheid-golf en 'n gepaardgaande periodiese versteuring van die kristalrooster ontwikkel. 'n Oorsig van die formasie van elektron diffraksiepatrone en wat ons daaruit kan leer word ook gegee. Daarna word die resultate van die ultravinnige elektron diffraksie eksperimente wat op 4Hb-TaSe2uitgevoer is beskryf en bespreek. In deel drie word 'n alternatiewe metode om die dinamika in kristalmonsters te bestudeer, naamlik laser plasma-gebaseerde ultravinnige X-straal diffraksie, beskryf. Die ultravinnige elektron diffraksie groep funksioneer as 'n eenheid, maar my verantwoordelikhede het gestrek van die voorbereiding van monsters en die karakterisering van die elektron bundel tot die opstel en uitvoer van eksperimente. Ek was ook betrokke by die analisering van data en het dele van die data analise sagteware geskryf.

At the heart of high harmonic generation lies a combination of optical and collision physics entwined by a strong laser field. An electron, initially tunnel-ionized by the field, driven away then back in the continuum, finally recombines back to rest in its initial ground state via a radiative transition. The emitted attosecond (atto=10^-18) XUV light pulse carries all the information (polarization, amplitude and phase) about the photorecombination continuum-to-ground transition dipolar field. Photorecombination is related to the time-reversed photoionization process. In this perspective, high-harmonic spectroscopy extends well-established photoelectron spectroscopy, based on charged particle detection, to a fully coherent one, based on light characterization. The main achievement presented in this thesis is to use high harmonic generation to probe femtosecond (femto=10^-15) chemical dynamics for the first time. Thanks to the coherence imposed by the strong driving laser field, homodyne detection of attosecond pulses from excited molecules undergoing dynamics is achieved, the signal from unexcited molecules acting as the reference local oscillator. First, applying time-resolved high-harmonic spectroscopy to the photodissociation of a diatomic molecule, Br2 to Br + Br, allows us to follow the break of a chemical bond occurring in a few hundreds of femtoseconds. Second, extending it to a triatomic (NO2) lets us observe both the previously unseen (but predicted) early femtosecond conical intersection dynamics followed by the late picosecond statistical photodissociation taking place in the reaction NO2 to NO + O. Another important realization of this thesis is the development of a complementary technique to time-resolved high-harmonic spectroscopy called LAPIN, for Linked Attosecond Phase INterferometry. When combined together, time-resolved high-harmonic spectroscopy and LAPIN give access to the complex photorecombination dipole of aligned excited molecules. These achievements lay the basis for electron recollision tomographic imaging of a chemical reaction with unprecedented angstrom (1 angstrom= 0.1 nanometer) spatial resolution. Other contributions dedicated to the development of attosecond science and the generalization of high-harmonic spectroscopy as a novel, fully coherent molecular spectroscopy will also be presented in this thesis.

The main topic of this thesis is the development of novel diagnostics for the characterisation of infrared femtosecond and extreme-ultraviolet (XUV) attosecond pulses. High-resolution interferometric methods are applied to high harmonic radiation, both to measure the properties of the XUV light and to relate this information to the physics of the fundamental generation process. To do so, a complete high harmonic beamline has been built and optimised to enable the observation of strong signatures of the macroscopic response of the medium. The distinct spatial characteristics of long and short trajectories are studied, as well as the interference between them. An interferometric measurement allows the extraction of the atomic dipole phase, which gives direct access to the sub-cycle electron dynamics. A major focus of this thesis is on the development of a novel method which simultaneously characterises two independent electric fields as a function of any degree of freedom in which it is possible to shear one of the beams. Since each field alternately takes the role of the reference to retrieve the other field, this technique is referred to as mutual interferometric characterisation of electric-fields (MICE). One of the key features of MICE is that no sheared but otherwise identical replica of the test pulse needs to be generated, which is a typical requirement of self-referencing techniques. Furthermore, no a priori information is needed for the reconstruction. The strength and the wide applicability of MICE are demonstrated using two fundamentally different examples. First, the temporal pulse profiles of two infrared femtosecond pulses are simultaneously reconstructed in a single laser shot. In the second demonstration, the MICE approach is used to simultaneously reconstruct the wavefronts of two high harmonic beams. Having this new technique at hand, the phase properties of the different quantum trajectories are compared. All pulse characterisation techniques implicitly assume full coherence of the beam. This, however, is often not the case in practice, in particular when dealing with complex XUV light sources. Here the standard characterisation techniques fail to provide an accurate description of the electric field. Instead, the electric field must be seen as a statistical mixture of different contributions to the overall field. Here an interferometric experiment is first proposed and then performed involving multiple lateral shears to measure the two-point correlation function of high harmonic radiation. This directly provides information about the existence and the magnitude of partial coherence of high harmonics.