Nanosecond Repetitively Pulsed (NRP) discharges in atmospheric pressure air have many potential applications. Spark NRP discharges have applications in plasma assisted combustion. These discharges tend to stabilize lean flames which produce less NOx. Furthermore, an increase of several hundreds of Kelvins in less than 20 ns has been observed following NRP spark discharges, which could be used to create nanomaterials. NRP glow discharges, while creating an important number of actives species such as atomic oxygen, do not heat the ambient gas, which allows them to be used in temperature-sensitive applications such as bio-decontamination. In the first part of this thesis, we validate experimentally the mechanism that was proposed to explain the ultrafast heating observed. Time-resolved measurements of the absolute densities of two excited states of nitrogen and of the gas temperature have been performed with calibrated Optical Emission Spectroscopy. The second part of the thesis deals with the NRP glow regime. We have shown that its existence depends on several parameters, gas temperature and pressure, voltage across the electrodes, inter-electrode distance, pulse duration, radius of curvature of the electrodes. This regime had not been observed for temperatures lower than 750 K so far. Thanks to a detailed parametrical experimental study and the analysis of the obtained results, we have succeeded in identifying the NRP glow regime at ambient temperature and we observe a new type of "multi-channel" glow regime.

We study multi-photon ionization of rare gas atoms and small molecules by infrared femtosecond laser pulses. We demonstrate that ionization is accurately described by a tunnelling model when many infrared photons are absorbed. By measuring photo-electron and photo-ion spectra, we show how the sub-Ångstrom spatial resolution of tunnelling gives information about electron densities in the valence shell of atoms and molecules. The photo-electron and photo-ion momentum distributions are recorded with a velocity map imaging (VMI) spectrometer. We describe a tomographic method for imaging a 3-D momentum distribution of arbitrary symmetry using a 2-D VMI detector. We apply the method to measure the 3-D photo-electron distribution in elliptically polarized light. Using circularly polarized light, we show how the photo-electron momentum distribution can be used to measure the focused laser intensity with high precision. We demonstrate that the gradient of intensities present in a focused femtosecond pulse can be replaced by a single average intensity for a highly nonlinear process like multi-photon ionization. By studying photo-electron angular distributions over a range of laser parameters, we determine experimentally how the photon linear momentum is shared between the photo-electron, photo-ion and light field. We find the photo-electron carries only a portion of the total linear momentum absorbed. In addition we consider how angular momentum is shared in multi-photon ionization, and find the photo-electron receives all of the angular momentum absorbed. Our results demonstrate how optical and material properties influence the photo-electron spectrum in multi-photon ionization. These will have implications for molecular imaging using femtosecond laser pulses, and controlling the initial conditions of laser generated plasmas.

Diffractive optical elements (DOEs) serve an important function in many dynamic and static optical systems. The theory and design of surface diffractive structures are well understood and practically applied at high spatial and phase resolution for a wide range of optical applications in science and industry. However, these structures normally only harness phase modulation of uniform fields for the beam diffraction and therefore limit their range of application, as well as being susceptible to surface damage. Multilayered volume diffractive elements offer a powerful opportunity to harness both phase and amplitude modulation for benefits in diffraction efficiency and beam shaping. However, multilayered combinations have been difficult to fabricate and provide only weak diffraction for phase gratings with low refractive index contrast. The advent of femtosecond laser writing inside transparent media has enabled the facile embedding of optical devices such as waveguides and diffractive optics into novel three-dimensional geometries that offer advanced functionality with compact design. In this work, femtosecond laser writing is pushed to the limits of forming high resolution phase elements with sufficiently strong refractive index contrast on which to develop volume phase gratings with the highest diffractive efficiency. The formation of both positive and negative zones of refractive index contrast together with rapid Talbot self imaging inside weakly contrasting phase gratings are major challenges here diminish the efficiency of assembled gratings. A method of strategic layering of otherwise weakly diffracting gratings onto Talbot planes is introduced to demonstrate, in FDTD models, the definitive enhancement of overall diffraction efficiency. A systematic optimization of laser writing in fused silica verify this enhancement or diminishment with weak volume gratings assembled on aligned or misaligned on Talbot planes. Advanced laser beam control methods were further demonstrated that underpin new direction for the facile assembly of highly functional DOEs that can exploit coherent light diffraction for opportunities in improving the performance of holographic devices and extend further to the powerful combination of phase and amplitude modulation control that is potentially available in a single optical device, thereby opening new directions for the design and fabrication of robust and strongly diffracting volume optical devices.

Diffractive optical elements (DOEs) serve an important function in many dynamic and static optical systems. The theory and design of surface diffractive structures are well understood and practically applied at high spatial and phase resolution for a wide range of optical applications in science and industry. However, these structures normally only harness phase modulation of uniform fields for the beam diffraction and therefore limit their range of application, as well as being susceptible to surface damage. Multilayered volume diffractive elements offer a powerful opportunity to harness both phase and amplitude modulation for benefits in diffraction efficiency and beam shaping. However, multilayered combinations have been difficult to fabricate and provide only weak diffraction for phase gratings with low refractive index contrast. The advent of femtosecond laser writing inside transparent media has enabled the facile embedding of optical devices such as waveguides and diffractive optics into novel three-dimensional geometries that offer advanced functionality with compact design. In this work, femtosecond laser writing is pushed to the limits of forming high resolution phase elements with sufficiently strong refractive index contrast on which to develop volume phase gratings with the highest diffractive efficiency. The formation of both positive and negative zones of refractive index contrast together with rapid Talbot self imaging inside weakly contrasting phase gratings are major challenges here diminish the efficiency of assembled gratings. A method of strategic layering of otherwise weakly diffracting gratings onto Talbot planes is introduced to demonstrate, in FDTD models, the definitive enhancement of overall diffraction efficiency. A systematic optimization of laser writing in fused silica verify this enhancement or diminishment with weak volume gratings assembled on aligned or misaligned on Talbot planes. Advanced laser beam control methods were further demonstrated that underpin new direction for the facile assembly of highly functional DOEs that can exploit coherent light diffraction for opportunities in improving the performance of holographic devices and extend further to the powerful combination of phase and amplitude modulation control that is potentially available in a single optical device, thereby opening new directions for the design and fabrication of robust and strongly diffracting volume optical devices.

In this thesis, I have developed a tunable two-color two-stage ultrafast Yb:fiber chirped pulse amplifier for the generation of short-pulse mid-infrared (MIR) radiation in the long-wavelength side of the "molecular fingerprint" (2.5-25 μm) using difference frequency generation (DFG) technique. The two colors called blue and red are in the wavelengths 1.03-1.11 μm and are amplified simultaneously in the same Yb-doped fiber amplifier (YDFA) stages in order to reduce the induced environmental noise on the phase difference of the pulses and to minimize the complexity and system cost. I will present numerical simulations on the two-stage YDFA system to amplify a two-color spectrum in the wavelengths 1.03-1.11 μm. The first and second YDFA called preamplifier and main amplifier are single-clad, single-mode and double-clad, single-mode YDFA respectively. From numerical simulations, the optimal length of the preamplifier to have equal power at two colors centered at 1043 nm and 1105 nm are in agreement with experimental results. It is well known that the power of MIR radiation generated by difference frequency mixing of two wavelengths scales up with the product of mixing powers in a fixed-field approximation. Furthermore, for the gain narrowing effect on the short-wavelength side of the YDFA gain profile, the spectral bandwidth of the blue color decreases resulting in pulse broadening. In addition, for the two colors separated largely, the amplified spontaneous emission is intensified. Considering the cited factors, I will present the modeling results on the two-color, two-stage YDFA system that the product of the power of the two colors is maximized for a maximized wavelength separation between the two mixing colors and a minimized gain narrowing on the blue color in order to build an as broadly tunable and powerful as possible ultrafast mid-infrared source by difference frequency mixing of the two colors. In this research, I achieved a wavelength separation as broad as 71 nm between pulses centered at 1038 nm and 1109 nm from the two-color ultrafast YDFA system. I achieved combined average powers of 2.7 W just after the main amplifier and 1.5 W after compressing the two-color pulses centered at 1041 nm and 1103 nm to nearly Fourier transform limited pulses. From autocorrelation measurements, the full width at half maximum (FWHM) of the compressed two-color pulses with the peak wavelengths of 1041 nm and 1103 nm was ~500 fs. By mixing the tunable two-color pulses in a 1-mm-thick GaSe crystal using DFG technique, I achieved tunable short-pulse MIR radiation. In this research, I achieved short-pulse MIR radiation tunable in the wavelengths 16-20 μm. The MIR tuning range from the lower side was limited to the 16 μm because of the 71-nm limitation on the two-color separation and from the upper side was limited to the 20 μm because of the 20-μm cutoff absorption wavelength of GaSe. Based on measured MIR spectra, the MIR pulses have a picosecond pulse duration in the wavelengths 16-20 μm. The FWHM of measured spectra of the MIR pulses increases from 0.3 μm to 0.8 μm as the MIR wavelength increases from 16 μm to 20 μm. According to Fourier transform theory, the FWHM of the MIR spectra corresponds to the bandwidth of picosecond MIR pulses assuming that the MIR pulses are perfectly Fourier-transform-limited Gaussian pulses. In this research, I achieved a maximum average power of 1.5 mW on short-pulse MIR radiation at the wavelength 18.5 μm corresponding to the difference frequency of the 500-fs two-color pulses with the peak wavelengths of 1041 nm and 1103 nm and average powers of 1350 mW and 80 mW respectively. Considering the gain bandwidth, Ti:sapphire is a main competitor to the YDFA to be used in the two-color ultrafast laser systems. In the past, the broad gain bandwidth of Ti:sapphire crystal has resulted in synchronized two-color pulses with a wavelength separation up to 120 nm. Apart from its bulkiness and high cost, Ti:sapphire laser system is limited to a watt-level output average power at room temperature mainly due to Kerr lensing problem that occurs at high pumping powers. In comparison, YDFA as a laser amplifier has a narrower gain bandwidth but it is superior in terms of average power. Optical parametric generation (OPG) and optical parametric amplification (OPA) techniques are two competitors to DFG technique for the generation of short-pulse long-wavelength MIR radiation. Although OPG offers a tunability range as broad as DFG, the MIR output power is lower because of the absence of input signal pulses. From the OPA technique, the tunability range is not as broad as the DFG technique due to limitations with the spectral bandwidth of the optical elements. Currently, quantum cascade lasers (QCLs) are the state-of-art MIR laser sources. At the present time, the tunability range of a single MIR QCL is not as abroad as that achieved from the DFG technique. More, mode-locked MIR QCLs are not abundant mainly because of the fast gain recovery time. Thus, the generation of widely tunable short-pulse MIR radiation from DFG technique such as that developed in this thesis remains as a persistent technological solution. The application of the system developed in this thesis is twofold: on one hand, the tunable two-color ultrashort pulses will find applications for example in pump-probe ultrafast spectroscopy, short-pulse MIR generation, and optical frequency combs generation. On the other hand, the short-pulse MIR radiation will find applications for example in time-resolved MIR spectroscopy to study dynamical behavior of large molecules such as organic and biological molecules.

An algorithm for extracting event information from a Coulomb Explosion Imaging (CEI) position sensitive detector (PSD) is developed and compared with previously employed schemes. The PSD is calibrated using a newly designed grid overlay and validates the quality of the described algorithm. Precision calculations are performed to determine how best the CEI apparatus at The University of Waterloo can be improved. An algorithm for optimizing coincidence measurements of polyatomic molecules in CEI experiments is developed. Predictions of improved efficiency based on this algorithm are performed and compared with experiments using a triatomic molecule. Analysis of an OCS targeted CEI experiment using highly charged Argon ions to initiate ionization is performed. The resulting measurements are presented using a variety of visualization tools to reveal asynchronous and sequential fragmentation channels of OCS3+.

In this thesis a powerful and practical method for characterizing ultrashort pulses in space and time is described (called SEA TADPOLE). First we focus on measuring pulses that are spatially uniform but very complicated in time or frequency. We demonstrate and verify that SEA TADPOLE can measure temporal features as small as 30 femtoseconds over durations as long as 14 picoseconds. The spectral resolution of this device is carefully studied and we demonstrate that for certain pulses, we achieve spectral super resolution. We also develop and test an algorithm for measuring polarization shaped pulses with SEA TADPOLE. Our simple interferometer can even be used to measure the spatiotemporal electric field of ultrashort pulses at a focus. This is because SEA TADPOLE samples the field with an optical fiber which has a small core size. Therefore this fiber can be used to spatially sample the beam, so that the temporal electric field can be measured at every position to obtain E(x, y, z, t). The single mode fiber can be replaced with an NSOM (Near Field Scanning Optical Microscopy) fiber so that spatial resolution as low as 500nm (and possibly lower) can be achieved. Using this device we make the first direct measurements of the compete field of focusing ultrashort pulses. These measurement can be viewed as "snap shots" in flight of the focusing pulse. Also, for the first time, we have observed some of the interesting distortions that have been predicted for focusing ultrashort pulses such as the "forerunner" pulse, radially varying group delay dispersion, and the Bessel-like X-shaped pulse. We have also made the first direct measurements of the electric field of Bessel X-pulses and their propagation invariance is demonstrated. We also use SEA TADPOLE to study the "boundary wave pulses" which are due to diffraction.

Detailed understanding of electron transfer reactions is important in many aspects of chemistry, biology and solar energy conversion. The main aim of this thesis is to provide further insight into electron transfer through highly conjugated bridge structures. Towards this end, three series of donor-acceptor dyads have been studied, all using an oligo(1,4-phenylene-ethynylene) moiety as the bridge. A common theme in these series is that they explore the effects of having either an ethynylene or phenylene as the attachment group between the bridge and the donor or acceptor. Photophysical characterization of these dyads was carried out by means of time resolved laser spectroscopy. The results show that having an ethynylene as attachment group results in higher rates for bridge mediated electron and energy transfer compared to similar systems, where a phenylene was used. It was also found that most of the investigated systems show a fast back electron transfer. A notable exception is a zinc(II) phthalocyanine- gold(III) porphyrin dyad, where very fast photoinduced electron transfer (kPET = 1.0×1012 s-1) was followed by relatively slow back electron transfer (kBET = 1.0×109 s-1). A complementary DFT investigation indicated that the charge shifted state involves a reduction of the gold ion, rather than the porphyrin ring. This results in lower electronic coupling between the reduced gold porphyrin and the bridge and thus slower back electron transfer. A series of zinc porphyrin platinum acetylide dyads was used to explore the effects on electronic coupling of different attachments points on the porphyrin ring. For the investigated system it was found that linking at the meso-position results in an eight-fold increase in electron transfer rate compared to the β-position. In addition, a series of mixed valence compounds was used to investigate electronic coupling mediated by cross-hyperconjugated or cross-π-conjugated bridges. The results indicate coupling elements of 100-400 cm-1, with the cross-π-conjugated bridge having the largest coupling. A complementary TD-DFT study indicates that both through bond and through space coupling can be active in these systems. The relative contribution of these two mechanisms to the electronic coupling is highly conformer dependent.

付記する学位プログラム名: 京都大学卓越大学院プログラム「先端光・電子デバイス創成学」 / 京都大学 / 新制・課程博士 / 博士(理学) / 甲第23690号 / 理博第4780号 / 新制||理||1684(附属図書館) / 京都大学大学院理学研究科物理学・宇宙物理学専攻 / (主査)教授 田中 耕一郎, 教授 金光 義彦, 教授 柳瀬 陽一 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM

This thesis describes an experimental investigation of optical frequency conversion in isotropic semiconductor waveguides by use of several phase-matching approaches. Efficient, type I second harmonic generation of femtosecond pulses is reported in birefringently-phase-matched GaAs/Alox waveguides pumped at 2.01 μm. Practical second harmonic average powers of up to ~ 650 μW are obtained, for an average launched pump power of ~ 5 mW. This corresponds to a waveguide conversion efficiency of ~ 20 % and a normalized conversion efficiency of greater than 1000 % W−1cm−2. Pump depletion of more than 80 % is recorded. Second harmonic generation by type I, third order quasi-phase-matching in a GaAs- AlAs superlattice waveguide is reported for fundamental wavelengths from ~1480 to 1520 nm. Quasi-phase-matching is achieved through modulation of the nonlinear coefficient χ[sub](zxy)(2), which is realised by periodically tuning the superlattice bandgap. An average output power of ~25 nW is obtained for a launched pump power of < 2.3 mW. Type I second harmonic generation by use of first order quasi-phase-matching in a GaAs/AlAs symmetric superlattice waveguide is also reported, with femtosecond fundamental pulses at 1.55 μm. A periodic spatial modulation of the bulk-like second- order susceptibility χ[sub](zxy)(2) is realized using quantum well intermixing by As+ ion implantation. A practical second harmonic average power of ~1.5 μW is detected, for a coupled pump power of ~11 mW. Second harmonic generation through modal-phase-matching in GaAs/AlGaAs semiconductor waveguides is reported. Using femtosecond pulses, both type I and type II second harmonic conversion is demonstrated for fundamental wavelengths near 1.55 μm. An average second harmonic power of ~10.3 μW is collected at the waveguide output for a coupled pump power of < 20 mW. For a complete characterisation, the optical loss is measured in these nonlinear GaAs- based waveguides over the spectral range 1.3-2.1 μm in the infrared, by deploying a femtosecond scattering technique. Typical losses of ~5-10 dB/cm are measured for the best of the waveguides, while a systematic intensity and wavelength dependent study revealed the contribution of Rayleigh scattering and two photon absorption in the overall transmission loss.