Master of Science / Department of Physics / Carlos Trallero / This report presents the details of an electron time-of-flight (ETOF) spectrometer to be used for characterizing ultrafast electric field pulses. The pulses will range in pulse-duration from femtosecond to attoseconds and in wavelength from the far infrared (FIR) to the extreme ultra violet (XUV). By measuring the photoelectrons in the presence of two electric fields and their quantum interference we will be able to extract the amplitude and phase of the electric field. For XUV pulses this is the well-known streaking and Reconstruction of Attosecond Beating by Interference of Two-Photon Transition (RABITT) method. The ETOF is based on a set of tunable electrostatic lenses capable of detecting 0-150 eV electrons. In addition, we can selectively increase the photoelectron yield of the spectrum. The precise tuning of the electrostatic lens system is done with a Genetic Algorithm (GA) with an intensity fluctuation discriminator in the fitness.

In this thesis the nonlinear and nonequilibrium properties of graphene are experimentally investigated using degenerate four--wave mixing and time--resolved pump--probe spectroscopy. High quality exfoliated natural graphite and large area epitaxial graphene on silicon carbide are investigated with femtosecond and picosecond ultrafast pulses in the near--infrared. A bespoke technique for suspending exfoliated graphene is also presented. In Chapter 3, the third--order nonlinear susceptibility of graphene is measured for the first time and shows a remarkably large response. Degenerate four--wave mixing at near--infrared wavelengths demonstrates an almost dispersionless emission over a broad spectral range. Quantum kinetic theory is employed to estimate the magnitude of the response and is in good agreement with the experimental data. The large susceptibility enables high contrast imaging, with a monolayer flake contrast of the order 10^{7} times higher than for standard reflection imaging. The degenerate four--wave mixing technique is utilised in Chapter 4 to measure the interface carbon signal of epitaxially grown graphene on silicon carbide. Comparable third--order signal from the silicon carbide bulk prevents true interface imaging. Excluding the third--order emission from detection by elongating the emission to outside a band--pass filter range allows for pure interfacial luminescence imaging. Features within the two growth faces are investigated with Raman spectroscopy. Nonlinear measurements are an increasingly popular tool for investigating fundamental properties of graphene. Chapter 5 investigates the influence of ultrafast pulses on the nonlinear response of graphene. High instantaneous intensities at the sample are shown to reduce the nonlinear emission by a factor or two. Comparing the Raman peak positions, widths and intensities before and after irradiation points to a huge doping of the samples, of the order 500 meV. In Chapter 6 the relaxation of photoexcited carriers is measured via time--resolved pump--probe spectroscopy, where a layer dependence of hot phonon decay is observed. Single layer flakes are observed to relax faster than bilayers and trilayers, with an asymptote reached at approximately four layers. Removing the substrate and measuring fully suspended samples reveals the same trend, suggesting that substrate interactions are not the cause of the enhanced decay. The decay mechanism is therefore intrinsic to graphene, perhaps due to coupling to out--of--plane, flexural phonons. The thickness dependence of epitaxial graphene on silicon carbide is compared to that of exfoliated flakes where the layer dependence is not observed. Phonon relaxation times, however, are in good agreement. Predictions for future investigations into this novel material based on the works here are suggested in Chapter 7. Preliminary pump--probe measurements at high carrier concentrations are an example of such progress, which will offer an insight into further decay mechanisms in graphene.

No description available.

In the past several decades the technology for the creation and use of ultrashort pulses has progressed tremendously. Now, it is possible to generate laser pulses as short as a few femtoseconds in duration, and such pulses have been used for a wide range of applications. In addition, the means of measuring these pulses has progressed so rapidly. However, despite recent great advances in ultrashort-pulse measurement techniques, much remains to be done. In particular, pulse-measurement devices have relatively small wavelength-tuning ranges, and the phase-match is problematic for the pulses with a wide bandwidth such as supercontinuum. In this thesis, I will demonstrate a new pulse measurement technique which can phase-match ultra-broad bandwidth of super-continuum using transient grating frequency-resolved-optical-gating (TG FROG). Also, I will demonstrate a simplified device which can measure the UV ultra-short pulse using transient grating process, one of the third-order nonlinearity and can cover from UV to IR with the same arrangement.

Active plasmonics combines the manipulation of light on both sub-wavelength length and ultrashort time scales, a unique meld that holds promise for developments in many scientific fields. This thesis reports on a novel approach to ultrafast, all-optical control of grating-assisted excitation of surface plasmon polaritons based on opto-thermally modifying the optical properties of gold. In contrast to prior works, this approach results in plasmonic modulation on picosecond and even sub-picosecond time scales, and is compatible with modern, multi-GHz information processing technology. Finally, an analytic model is developed that allows for the rapid and accurate calculation of the coupling efficiency of beams with arbitrary spatial profile. First, the ultrafast dynamics of existing plasmonic coupling resonances, on gold films with grating overlayers, are studied with spectrally resolved pump-probe measurements. Irradiation of the metal by 700 fs, 775 nm laser pulses results in modulations of the plasmonic coupling efficiency of ~20% near the center, or ~60% off-center, of resonances centered between 540 nm and 700 nm. The modulations decay with a time constant of 770 +/- 70 fs. The experimental results are consistent with simulations based on the thermal-dynamics of the electron-lattice gold system, coupled with numerical modeling of light-grating interactions. Next, two 150 fs, 810 nm laser beams are interfered on the surface of a planar gold film, leading to an absorption/refraction grating in the metal. Optical pump-probe spectroscopy measurements of the first (-1) diffracted order in transmission identify plasmonic coupling resonances between 520 nm and 570 nm. The observed coupling efficiency is ~10^{-5}, and the launch window decays with a time constant of 620 +/- 100 fs. Lastly, a Green function-based analytic model is developed to describe grating assisted plasmonic coupling, culminating in a first-order differential equation with coefficients that have both clear physical significance as well as analytic forms. Comparison of this technique with standard numerical modeling methods shows that plasmonic coupling efficiencies in excess of 0.8 are predicted within an error of 15%. This model is used to study plasmonic excitation by finite-size beams, showing the spatial evolution of the intensity of both the surface plasmon polariton and the reflected beam.

Active plasmonics combines the manipulation of light on both sub-wavelength length and ultrashort time scales, a unique meld that holds promise for developments in many scientific fields. This thesis reports on a novel approach to ultrafast, all-optical control of grating-assisted excitation of surface plasmon polaritons based on opto-thermally modifying the optical properties of gold. In contrast to prior works, this approach results in plasmonic modulation on picosecond and even sub-picosecond time scales, and is compatible with modern, multi-GHz information processing technology. Finally, an analytic model is developed that allows for the rapid and accurate calculation of the coupling efficiency of beams with arbitrary spatial profile. First, the ultrafast dynamics of existing plasmonic coupling resonances, on gold films with grating overlayers, are studied with spectrally resolved pump-probe measurements. Irradiation of the metal by 700 fs, 775 nm laser pulses results in modulations of the plasmonic coupling efficiency of ~20% near the center, or ~60% off-center, of resonances centered between 540 nm and 700 nm. The modulations decay with a time constant of 770 +/- 70 fs. The experimental results are consistent with simulations based on the thermal-dynamics of the electron-lattice gold system, coupled with numerical modeling of light-grating interactions. Next, two 150 fs, 810 nm laser beams are interfered on the surface of a planar gold film, leading to an absorption/refraction grating in the metal. Optical pump-probe spectroscopy measurements of the first (-1) diffracted order in transmission identify plasmonic coupling resonances between 520 nm and 570 nm. The observed coupling efficiency is ~10^{-5}, and the launch window decays with a time constant of 620 +/- 100 fs. Lastly, a Green function-based analytic model is developed to describe grating assisted plasmonic coupling, culminating in a first-order differential equation with coefficients that have both clear physical significance as well as analytic forms. Comparison of this technique with standard numerical modeling methods shows that plasmonic coupling efficiencies in excess of 0.8 are predicted within an error of 15%. This model is used to study plasmonic excitation by finite-size beams, showing the spatial evolution of the intensity of both the surface plasmon polariton and the reflected beam.

Chiral molecules are composed of the same constituent atoms, but are inherently different due to being mirror images of each other. The physical properties of such molecules are nearly identical, but the biochemical interactions can differ wildly, which has extreme implications in the pharmaceutical industry. It is for this reason that it is important to be able to characterize and study individual enantiomers, and develop physical methods to do so. Optical techniques have evolved over the past two decades of scientific work which have been shown to be able to distinguish one enantiomer from another. These techniques tend to involve the use of circularly polarized light to induce a forward/backward asymmetry along the axis of light's propagation. The resulting sensitivity difference between enantiomers is typically on the order of a few percent. Recently, a novel optical pulse scheme has been developed whose electric field is fully three-dimensional and inherently chiral. This field was computationally used to demonstrate that the signal difference between enantiomers can reach upwards of 100\% sensitivity through the generation of high harmonics. Presented in this thesis are the results of an experimental measurement performed using just such a novel pulse scheme. A cold target recoil ion momentum spectroscopy machine is used to detect the photoelectron spectra from the ionization of each enantiomer of propylene oxide. A comprehensive discussion on the practical realization of the novel pulse scheme is presented, and the circular dichroism due to the novel field is shown. Also discussed are fragmentation of propylene oxide, three dimensional chiral signals found in the data, and a new measure to define the magnitude of chirality in a photoelectron distribution. Finally, measurements pertaining to the ionic yield of each enantiomer under varying handedness of light are shown. These results are the first experimental realization of optical measurements using synthetically designed chirality.

No description available.

In the last decade, there has been tremendous progress in the field of ultrashort-pulse measurement. However, this effort has focused mostly on the temporal behavior of 100-fs, 800-nm ultrashort pulse, ignoring other pulse lengths, wavelengths, and the very common space-time couplings or so called spatio-temporal distortions. In this thesis work, I do an extensive study of spatio-temporal distortions and their measurement using Frequency Resolved Optical Gating (FROG) and its relatives. I clarify some ambiguities in the descriptions of these effects in the existing theory and establish a more general description of such distortions in ultrashort pulses. I also extend these measurement techniques to different wavelengths and pulse lengths. Specifically, I develop measurement devices for few-cycle NIR pulses, weak and narrowband fiber laser pulses, long (several-ps) NIR pulses, and visible pulses from NOPAs.

<p>This thesis focuses on femtosecond studies of relaxation and photo-induced dissociation processes in the liquid environment. Measurements are performed using both polarization sensitive and magic angle transient absorption spectroscopy with excitation wavelengths of 387 nm and 258 nm and a white light continuum probe.</p><p>In the first three papers the photodissociation of the trihalides I₃^- in acetonitrile and methanol as well as I₂Br^- in acetonitrile solution is investigated. These studies address such issues as the time scale for the production of the main photoproduct I₂^-, rotational dynamics of the formed diatomic anions, the subsequent wavepacket dynamics of the coherently excited diiodide anion and vibrational relaxation in, and the geminate recombination of, the I₂^-fragment. A nearly equal, bent geometry for the parent anion at the moment of bond breakage is proposed in all three solutions. However, the rotational temperature of the diiodide anion produced in the various solutions, reveals that motion along the bending coordinate of the dissociating triatomic anions plays an important role. The first signs of I₂^- fragments can already be observed at delays of approximately 130 – 190 fs which indicates a faster dissociation than suggested in earlier publications. The production of I₂^- seems fastest for I₃^- in methanol, followed by I₂Br^- in acetonitrile and is slowest for I₃^- in acetonitrile. It appears that vibrational relaxation of newly formed I₂^- fragments happens on a short time scale of a few hundred femtoseconds from initially excited vibrational states centered around v = 60 to v = 20. This fast relaxation was never directly observed before in solution. After that it relaxes with a slower time constant of approximately 2 ps which is shorter than most former reported values. This biexponential behavior agrees well with earlier molecular dynamics simulations. The dependence of the dissociation product formation on excitation energy, parent anion and solvent is found to be relatively strong. These findings lead us to believe that the photo-induced dissociation of the triatomic anions I₃^- and I₂Br^- in solution may very well resemble the gas phase process more than previously thought.</p><p>In paper IV electronic and vibrational relaxation rates of the cyanine dye Methyl-DOTCI are determined after excitation to high lying electronic states. The measurements are performed with two different excitation wavelengths and in various solvents. They reveal a fast electronic relaxation to the second excited electronic state which subsequently relaxes to the first excited electronic state with a time constant of about 10 ps. This relatively long relaxation time may partly be explained by the badly overlapping electronic wavefunctions obtained from theoretical calculations. Vibrational relaxation proceeds with a similar time constant of 10 ps but shows a marked solvent dependence with faster relaxation rates in alcohol solutions.</p>