An experimental apparatus has been constructed to investigate ionisation mechanisms of complex molecules and nanoparticles after femtosecond and/or picosecond laser excitation. The photoproducts are detected by time-of-flight mass spectrometry and velocity-map imaging (VMI) photoelectron spectroscopy. Test measurements on C60 and Xe have successfully reproduced previously published work indicating that the setup is working in a satisfactory manner. New detailed investigations of mass spectra and angle resolved photoelectron spectra (PES) have been carried out as a function of laser intensity, wavelength and pulse duration for C60 and C70, providing new insights into the electronic structure and ionisation mechanisms of these molecules. For 400 nm, 130 fs laser excitation, an isotropic contribution from thermally emitted electrons is found. A series of peaks are seen superimposed on the thermal background with binding energies in agreement with the recently discovered superatom molecular orbitals (SAMOs) of C60 [Feng et.al. Science 320 (2008) p. 359]. Furthermore, the angular dependence of the peak in the PES corresponding to the s-SAMO is in agreement with this assignment. To confirm the assignment of the other observed peaks it is concluded that the measured photoelectron angular distributions (PADs) need to be compared to calculated angular distributions. Measurements have also been made with the same wavelength but with a pulse duration of about 5 ps. Mass spectra, PES and PADs for these measurements show that the main ionisation mechanism for these laser conditions is delayed (thermionic) ionisation. For 800 nm, 130 and 180 fs laser excitation, thermally emitted electrons are observed. In contrast to the 400 nm measurements, the PADs show an asymmetry with higher apparent temperatures along the laser polarisation direction. Measurements were also made for longer pulse durations (1.0 – 3.8 ps). For pulse durations above 1 ps the asymmetry is gradually reduced while the delayed ionisation component in the mass spectrum increases with increasing pulse duration. The asymmetry is compared to calculations made assuming a field-assisted thermal electron emission. Similarly to the 400 nm experiments, a series of peaks are seen superimposed on the thermal background. PADs are presented for these peaks. PADs for peaks with the same binding energy as peaks seen in the 400 nm experiments follow the same trend. Isotropic PADs after ns laser excitation are also presented confirming delayed ionisation for these pulse durations.

This thesis is concerned with describing a novel technique for characterizing the (spectrally resolved) spatial properties of light. The new approach, known as Scanning Interference Method for Integrated Transverse Analysis of Radiation (SCIMITAR), is a specific implementation of a variable-separation two-pinhole interferometer. Evaluation of the series of interference patterns produced by a SCIMITAR measurement allows the transverse profiles of intensity and spatial phase to be retrieved, while at the same time characterizing the spatial coherence of light. Including a diffraction grating in the simple experimental arrangement permits the spectral dependence of the aforementioned quantities to be measured. The SCIMITAR technique was demonstrated by characterizing the spatial properties of high harmonic generation (HHG). Excellent agreement with an alternate characterization technique known as SWORD was observed. The spectral dependence of the harmonic spatial properties was also investigated. Evidence suggesting absorption may play a role in shaping the harmonic intensity and spatial coherence was presented. Treating the harmonic radiation as either a fully coherent or partially coherent beam allowed the intensity width, spatial phase curvature and coherence width of the harmonic radiation source to be deduced. Measurement of the fine variation of the harmonic complex coherence factor (CCF) with pinhole separation revealed distinctive modulations. The Van Cittert-Zernike theorem was modified by including a Gerchberg-Saxton inspired improvement, allowing data missing from the SCIMITAR measurement to be inferred. The harmonic equivalent incoherent source intensity profile was found to be asymmetric with low intensity features isolated away from the optical axis. Calculations of the diffraction pattern produced by illumination of a non-redundant array of pinholes showed that the modulated harmonic properties could adversely influence lensless imaging-type experiments.

As a type of nonlinear system with complexity, mode-locked fiber lasers are known for their complex behaviour. It is a challenging task to understand the fundamental physics behind such complex behaviour, and a unified description for the nonlinear behaviour and the systematic and quantitative analysis of the underlying mechanisms of these lasers have not been developed. Here, we present a complexity science-based theoretical framework for understanding the behaviour of mode-locked fiber lasers by going beyond reductionism. This hierarchically structured framework provides a model with variable dimensionality, resulting in a simple view that can be used to systematically describe complex states. Moreover, research into the attractors' basins reveals the origin of stochasticity, hysteresis and multistability in these systems and presents a new method for quantitative analysis of these nonlinear phenomena. These findings pave the way for dynamics analysis and system designs of mode-locked fiber lasers. We expect that this paradigm will also enable potential applications in diverse research fields related to complex nonlinear phenomena.

Ultra-short and high-peak-power laser pulses have important industrial and scientific applications. While direct laser amplification can lead to peak powers of several million watts, higher values than these cannot be achieved without causing damage to the amplifier material. Chirped pulse amplification technique is thus invented to break this barrier. By temporally stretching pulses before entering amplifier, the pulse peak power is significantly reduced and thus becomes safe to be passed through the amplifier. After amplification, a compressor is used to recover the pulse width, and high-power ultra-short laser pulses are produced. Chirped pulse amplification technology increases the pulse energy by transferring the damaging effects of high-peak power laser pulses from the vulnerable amplifier to a relatively robust compressor system. The compressor is therefore a crucial device for producing high peak powers. However, there are some major drawbacks associated with it. First, compressors in high-energy laser system are usually over 1 cubic meter in size. For many applications, this large and cumbersome size is a limiting factor. Second, compressors are sensitive to outside disturbances; a little misalignment can lead to failure of pulse compression process. Third, gratings with large uniformly ruled area are difficult to fabricate, which impose a limit on achievable peak powers and pulse durations of laser pulses through the use of conventional compressors. In this project, we present a grating-based monolithic optical compressor that offers a way around some of the major problems of existing compressors. By integrating the key optical components, one can make a robust and monolithic compressor that requires no alignment. In the new scheme, folding the optical path with reflective coatings allows one to design a compressor of significantly reduced size by minimizing both the longitudinal and transverse dimensions of the device. The configuration and operation mechanism of this novel compressor are described. A method for calculating the volume of the compressor is investigated. This is validated by computing the size of a specific monolithic compressor. Simulation results obtained through finite-difference time-domain method are presented, proving that the new compressor provides a compact, portable, and robust means for temporally compressing long duration pulses.

Doctor of Philosophy / Department of Industrial & Manufacturing Systems Engineering / Shuting Lei / Lasers have been widely used as a manufacturing tool for material processing, such as drilling, cutting, welding and surface texturing. Compared to traditional manufacturing methods, laser-based material processing is high precision, can treat a wide range of materials, and has no tool wear. However, demanding manufacturing processes emerging from the needs of nano and 3D fabrication require the development of laser processing strategies that can address critical issues such as machining resolution, processing speed and product quality. This dissertation concerns the development of novel laser processing strategies based on spatial, temporal and spectral control of light-matter interaction. In the spatial domain, beam shaping is employed in ultrafast laser micro-processing. Zero-order Bessel beam, generated by an axicon, is used for selective removal of the back contact layer of thin film solar cells. Bessel beam’s propagation-invariance property gives rise to an extension of focal range by orders of magnitude compared to Gaussian beam, greatly increasing process tolerance to surface unevenness and positioning error. Together with the axicon, a spatial light modulator is subsequently used to modify the phase of laser beam and generate superpositions of high-order Bessel beam with high energy efficiency. With the superposed beam, processing speed can be increased significantly, and collateral damage resulting from the ring structures in the zero-order Bessel beam can be greatly suppressed. In the temporal domain, it is demonstrated that ionization in dielectric materials can be controlled with a pair of ultraviolet and infrared pulses. With the assistance of the long-wavelength infrared pulse, nano-scale features are achieved using only a small fraction of threshold energy for the short-wavelength pulse. Computer simulation based on the rate equation model is conducted and found to be in good agreement with experimental results. This study paves the way for future adoption of short-wavelength laser sources, for example in the extreme ultraviolet range, for direct laser nano-fabrication with below-threshold pulse energy. In the spectral domain, a short-wavelength infrared laser is used to generate modification in the bulk of silicon wafers, in an attempt to develop 3D fabrication capabilities in semiconductors. Issues such as spherical aberration correction and examination procedure are addressed. Permanent modification is generated inside silicon by tightly focusing and continuously scanning the laser beam inside the samples, without introducing surface damage. The effect of laser pulse energy and polarization is also investigated. These results demonstrate the potential of controlling laser processing in multiple dimensions for manufacturing purposes, and point to a future when laser can be used as naturally and efficiently as mechanical tools used today, but is targeted at more challenging problems.

Dans cette thèse, différentes méthodes de dynamique quantique basées sur la propagation de trajectoires sont développées. La première approche consiste en une développer global des champs hydrodynamiques sur une base de polynômes de Chebyshev. Ce schéma est utilisé pour étudier la dynamique vibrationnelle unidimensionnelle de paquets d'ondes dans des potentiels harmoniques et anharmoniques. Par la suite, une méthodologie différente est développée, qui, à partir d'un paramétrage précédemment proposé pour la densité quantique, permet de construire des potentiels d'interaction effectifs entre les pseudo-particules représentant la densité. Dans le cadre de cette approche, plusieurs problèmes de modélisation sont étudiés et des effets quantiques importants sont décrits, tels que l'énergie de point zéro, l'effet tunnel, la diffusion et la réflexion sur une barrière. La même approximation est utilisée pour l'étude de l'ionisation des atomes par laser. Dans une troisième approche, un potentiel quantique approximatif à plusieurs corps est dérivé pour décrire des matrices d'argon et de krypton contenant une impureté de sodium. Il est obtenu en proposant un ansatz approprié pour la fonction d'onde de l'état fondamental du solide. Le potentiel est utilisé dans les simulations de dynamique moléculaire pour obtenir les spectres d'absorption de l'atome de Na isolé dans les matrices cryogéniques. / In this thesis different trajectory-based methods for the study of quantum mechanical phenomena are developed. The first approach is based on a global expansion of the hydrodynamic fields in Chebyshev polynomials. The scheme is used for the study of one-dimensional vibrational dynamics of bound wave packets in harmonic and anharmonic potentials. Furthermore, a different methodology is developed, which, starting from a parametrization previously proposed for the density, allows the construction of effective interaction potentials between the pseudo-particles representing the density. Within this approach several model problems are studied and important quantum mechanical effects such as, zero point energy, tunneling, barrier scattering and over barrier reflection are founded to be correctly described by the ensemble of interacting trajectories. The same approximation is used for study the laser-driven atom ionization. A third approach considered in this work consists in the derivation of an approximate many-body quantum potential for cryogenic Ar and Kr matrices with an embedded Na impurity. To this end, a suitable ansatz for the ground state wave function of the solid is proposed. This allows to construct an approximate quantum potential which is employed in molecular dynamics simulations to obtain the absorption spectra of the Na impurity isolated in the rare gas matrix.

Cytoglobin (Cygb) and neuroglobin (Ngb) are among the newest members of vertebrate globin family characterized by a classical 3-over-3 α-helical fold and a heme prosthetic group capable of reversibly binding small ligands such as O2, CO and NO. The physiological functions of Cygb and Ngb remain to be determined; however, current data suggest that both proteins have a significant role in cytoprotection in hypoxic and genotoxic conditions. Cytoglobin and Ngb are distinct from their better-known counterparts, hemoglobin (Hb) and myoglobin (Mb), in several structural features. First, in the absence of an external ligand, the sixth coordination site of the heme iron in Cygb and Ngb is occupied by a distal histidine residue, leading to a complex ligand rebinding mechanism dependent on the rate of distal His dissociation from the heme iron. Although hexacoordination was observed before in plant and bacterial hemoglobins, the physiological role of this feature remains unknown. Second, both Ngb and Cygb are capable of forming an intraprotein disulfide bond, which has been shown to regulate ligand binding affinity, leading to a hypothesis that intracellular function of these proteins is redox-dependent. Lastly, Cygb contains 20 amino acid long extensions on both N- and C- termini, a unique feature among vertebrate globins with unknown physiological function. The work presented in the dissertation reveals that hexacoordinate heme reactivity is distinct from that of pentacoordinate heme and is strongly influenced by the distal histidine residue and the disulfide bond. In the case of human Cygb, experimental and computational approaches demonstrated that the disulfide bond regulates the flexibility of the N terminus and the accessibility of the 1,8-ANS binding site. Furthermore, molecular dynamics of the hexa- and pentacoordinate human Ngb were probed computationally to elucidate structural requirements that govern signal transmission between CD loop and the distal pocket. Lastly, Ngb and Cygb were reconstituted with a fluorescent analog of the native heme group to produce hexacoordinate variants with favorable photophysical properties that can be used to characterize protein-protein interactions.

In the past decade, ultrashort laser sources have had a decisive impact on material processing for photonic applications. The technique is usually restricted to the elemental association of an ultrashort source with a focusing lens. It is thus limited in the achievable bulk modifications. Accompanying studies of material modifications in space and time, we propose here that automated spatio-temporal tailoring of the laser pulses is an efficient manner to overcome these limitations. More precisely, we demonstrate the generation of multiple processing foci for synchronous photomachining of multiple devices in the bulk. Thus, we report on the parallel photowriting of waveguides, light couplers, light dividers in 2D/3D in fused silica glass. We show that the domain of photowriting can be extended to deep focusing. We indicate that this can be achieved by wavefront shaping or temporal profile tailoring conducted by an evolutionary optimization loop. We also have unveiled a singular interaction regime where regular structuring takes place before the focal region. For the first time, the dynamics of the energy coupling to the glassy matrix is evaluated for various temporal pulse profiles. Enhanced energy confinement in the case of picosecond pulses is confirmed by characterization of the transient electronic gas and of the subsequent pressure. These pump-probe studies were carried out with a self-build time-resolved microscopy system with temporally shaped pump irradiation. We also developed a new method based on the Drude model to differentiate the electronic and matrix contributions to the contrast of the microscopy images.

We demonstrate experimentally that the multiphoton ionization rate in gallium arsenide depends on the alignment of the laser polarization with respect to the crystal axis. We show real-time modulation of 1900nm laser ionization rate, through viewing transmission, which mimics the symmetry of the semiconductor crystal. We propose that the modulation in the ionization rate arises because the varying reduced effective carrier mass, as predicted by Keldysh theory. We show direct comparison of the experimental transmission modulation depth with that predicted by Keldysh theory. This opens up a novel method for real-time non-invasive crystallography of crystalline materials.

The ultrafast optical regime is defined, as it applies to laser pulses, along with a brief introduction to pulse generation and characterisation technologies. A more extensive description of our particular amplified pulse generation and SPIDER characterisation systems follows. Data verifying the correct operation of the characterisation system is presented and interpreted. Our laser system is then characterised in two different configurations. In each case, the data describing the system is presented and analyzed. Conclusions are made regarding the performance of both the characterisation and laser systems, along with suggested improvements for each.