Bragg spaced quantum wells represent a unique class of resonant photonic materials, wherein a photonic bandgap is created by the periodic spacing of quantum wells and the associated variation in the complex susceptibility (index and absorption) of the material. Interest in BSQWs has grown in the past decade due to their large ultrafast nonlinearities and the corresponding large ultrafast reflectivity changes and transmissivity. These nonlinearities are of particular interest in areas of communication technology, where ultrafast all-optical logic components have become increasingly in demand. This research will further investigate BSQWs and the for the first time effects of spin-dependent nonlinear excitation on their photonic band structures. It will also investigate how these effects can be used in all-optical polarization switching and tunable optical buffer (slow light) applications.

Herein are presented collective studies of amino acid-based surfactants, also known as lipoamino acids, at liquid interfaces. Chapter III describes an investigation of domain morphology of N-Stearoylglutamic acid (N-SGA) Langmuir monolayers at the air/water interface by epifluorescence microscopy. Anisotropic feather-like domains were observed in L-enantiomeric monolayers while symmetric circular domains were found in racemic N-SGA monolayers. At a surface pressure of 30 mN/m the enantiomeric domains melted at 31 ??C while the racemic domains melted at 27 ??C. This result is exactly opposite to the behavior found in bulk crystals where the racemate melts at a higher temperature. These results were explained in terms of different molecular packing and hydrogen bonding between bulk crystals and two-dimensional thin films for enantiomeric and racemic compounds. Chapter IV summarizes the investigations of hydrogen bonding in N-acyl amino acid monolayers by vibrational sum-frequency spectroscopy (VSFS). The intermolecular hydrogen bonding interaction between the adjacent molecules through amide-amide groups in N-stearoylalanine (N-SA) is characterized by an NH stretch peak at 3311 cm-1. This is the first time that the amide NH stretching signals have been detected with the VSFS technique. A similar peak was detected at 3341 cm-1on N-SGA monolayer. The higher frequency indicates that the H-bond strength is weaker due to the larger size of the glutamic acid residue. The NH stretch mode can thus be used as a fingerprint of hydrogen bonding among amide-amide groups. A peak at 3050 cm-1 due to hydrogen bonding among carboxyl groups was also resolved from the VSFS spectra. Molecular models of intermolecular hydrogen bonding were proposed.

This thesis describes research on near degenerate quasi phase-matched opticalparametric oscillators (OPO) where volume Bragg gratings (VBG) are used toproduce narrow oscillation bandwidth. These OPOs are then used to pump a secondOPO to generate mid-infrared radiation. The atmospheric transmission windows in the 3.5 to 5 μm wavelength region areused for seekers on infrared homing missiles. These missiles are available to guerrillaand terrorist groups and have been used in a number of attacks on military and civilianaircraft. Laser sources at the same wavelengths are an important component incountermeasure systems for aircraft self-protection. Similar laser sources also haveapplications in laser surgery. At wavelengths longer than 4 μm crystal materials for multi-Watt level averagepower nonlinear devices is a problem. The best solution so far is to use ZnGeP2(ZGP). ZGP and the available alternatives all have a problem of near-infraredabsorption, and a mid-infrared OPO thus has to use a pump wavelength near 2 μm.This pump source can be a neodymium laser at 1.06 μm with a near degenerate OPO. Nonlinear devices for low to medium pulse energies are dominated by quasi phasematchedmaterials because of their higher effective nonlinearities and lack of walkoff.In addition they allow type I interaction where signal and idler from the OPOhave the same polarization, which has the advantage that both waves can be used topump the ZGP OPO. The drawback of this is that the near-degenerate interaction hasvery wide gain bandwidth. Efficient pumping of the second OPO demands narrowbandwidth output from the first OPO.Volume Bragg gratings that are glass materials with a periodic refractive indexmodulation have emerged as high quality narrow bandwidth reflectors. By using aVBG as one cavity mirror in an OPO the feedback bandwidth and hence the OPOoscillation bandwidth can be kept very narrow. Signal and idler bandwidths of 10 and20 GHz (FWHM) at 2122 and 2135 nm, respectively, have been demonstrated. Thisshould be compared to the several hundred nanometre bandwidth from an OPO usingdielectric mirrors. Very narrow bandwidth operation has been achieved so close todegeneracy that the signal and idler are not resolvable. The total output energy generated in the PPKTP OPO (signal and idler together)has been used to pump a ZGP OPO that produced mid-IR radiation. Tuning of thesignal from a ZGP OPO from 2.9 μm to degeneracy at 4.3 μm has been shown, with acorresponding idler wavelength tuneable up to 8 μm. The highest conversionefficiency that has been reached from 1.06 μm to the mid-IR was 12 %. This setupused a PPKTP OPO with 30 % conversion efficiency and 13 nm separation of signaland idler (2122 and 2135 nm). The pulse repetition frequency was 20 kHz and thegenerated output power in the mid-IR was 3.2 W. / QC 20100517

Silicon Nanowires (SiNWs) with ability to confine carriers and photons in two directions while allowing propagation in third dimension offer interesting modified optical properties such as increased material absorption and optical non-linearities with regard to that of bulk silicon. Enhanced optical properties in SiNWs open a window not only to improve the performance of existing devices but also to realize novel structures. As such, I chose to investigate SiNWs for their applications in photonics, especially for sensing and non-linear devices. My goal was to conduct fundamental research on the optical properties of these SiNWs, and then develop an integration platform to realize practical devices. The platform should be compatible with IC manufacturing. Electron Beam Lithography (EBL) using a Poly Methyl Methacrylate (PMMA) resist followed by Inductively Coupled Plasma Reactive Ion Etching (ICP-RIE) is used for SiNWs fabrication. Now we are able to fabricate nanowires as small as 15 nm in diameter with the smallest separation of 50 nm. In addition, the interface between SiNWs and Si substrate is optically smooth enabling us to fundamentally understand optical properties of these structures. During the course of this project, I have contributed new fundamental knowledge about SiNWs. For example, Second Harmonic Generation (SHG) is demonstrated in SiNWs, which is absent in bulk silicon. This is achieved by self-straining the nanowires and is the first demonstration of this kind. Second-order non-linearities are more efficient for optical signal processing than third-order ones (which have been used for silicon photonics devices so far). Therefore, these results open a new area of research in silicon. In addition to second order nonlinearity, high enhancement of Raman scattering is achieved in SiNWs fabricated on Silicon on Insulator (SOI) substrate. This can find promising applications in sensing and nonlinear based devices such as optical switches and logic gates. Further, polarization resolved reflections from these nanowire arrays were measured and significant differences were observed for the reflection characteristics for the sand p-polarized beams. In order to understand these reflections, an effective index model is proposed based on calculations using Finite Difference Time Domain (FDTD) method. Results of this analysis provide useful information for designing of many optical devices using SiNWs such as solar cells and photodetectors. As another part of this thesis, vivid colors in mutually coupled SiNWs is demonstrated where nanowire diameters range from 105 nm to 345 nm. A simple sensor is demonstrated by observing the change in the reflected color with changing refractive index of the surrounding medium. A refractive index resolution of 5×10−5 is achieved using a simple charge coupled device (CCD) camera. Although, there were some paradigm shifting results during my fundamental studies, it became very apparent that SiNWs suffer from a major issue inhibiting their use in photonics devices. Below the diameter of 100 nm where these enhanced material properties were observed, SiNW is a poor optical waveguide with less than 1 % of light confined. The low confinement factor means that though the intrinsic properties of SiNWs increase, the overall device performance is not significantly enhanced. To overcome this issue, a new platform technology is invented, called Silicon Nanowire Optical Waveguide (SNOW). It combines the material advantages of nanostructures with the optical properties of conventional waveguides, and consists of arrays of nanowires in close proximity. It is shown that such a structure can guide an optical mode using the FDTD method. This waveguide structure can be used as a versatile platform to manufacture various devices such as sensors, switches, modulators, grating, and delay lines. For instance, a novel bio-sensor is proposed and designed whose sensitivity is enhanced by a factor of 20, compared to conventional silicon-wire waveguides.

The lateral spatial separation between the circular polarization components of a linearly polarized light beam impinging at off-normal incidence on an air-semiconductor interface is investigated experimentally and theoretically. This fundamental optical phenomenon is referred to as the Spin Hall effect of light (SHEL). An optical pump-probe technique is demonstrated to resolve in situ the nanometer size SHEL displacement of a beam transmitted inside an absorptive material. Three different types of optical interactions in silicon and GaAs demonstrate the technique’s general applicability. First, resonant ∼150 fs pump and probe pulses at λ = 820 nm resolve the SHEL displacement via free-carrier absorption in a 10 μm thick silicon sample. The measured SHEL displacements for a p-polarized probe beam are obtained between −10 to 150 nm as a function of the angle of incidence on the sample. Different angles of incidence are achieved by keeping a fixed angular separation between the pump and the probe beams while rotating the sample about the axis perpendicular to the plane of incidence. In another experiment, an optically thin (500 nm thick) GaAs sample allows one to use Pauli-blocking as an optical interaction to investigate the polarization and angular dependence of the SHEL in the probe beam. For such a polarization-dependent imaging technique, the SHEL displacement in the pump beam also contributes to the measured signal and is evaluated experimentally. A probe beam at normal incidence is used to measure a SHEL displacement of ∼180 nm in a transmitted p-polarized pump beam impinging on the sample with an angle of incidence of 55 degrees. Finally, two-photon absorption is used to resolve the SHEL in a (001) oriented 500 μm thick GaAs wafer using an optical source generating sub-bandgap radiation (λ = 1550 nm) with a pulse duration of 120 fs. Linearly p- and s- co-polarized pump and probe beams are also used to investigate the polarization dependence of the SHEL. All the experimental results obtained using these different optical interactions agree with the theory within the experimental error. Finally, analytical expressions of the shifts experienced by the circular components of a beam impinging at an interface between two optical media are also derived for an incident beam with an arbitrary spatial distribution.

The lateral spatial separation between the circular polarization components of a linearly polarized light beam impinging at off-normal incidence on an air-semiconductor interface is investigated experimentally and theoretically. This fundamental optical phenomenon is referred to as the Spin Hall effect of light (SHEL). An optical pump-probe technique is demonstrated to resolve in situ the nanometer size SHEL displacement of a beam transmitted inside an absorptive material. Three different types of optical interactions in silicon and GaAs demonstrate the technique’s general applicability. First, resonant ∼150 fs pump and probe pulses at λ = 820 nm resolve the SHEL displacement via free-carrier absorption in a 10 μm thick silicon sample. The measured SHEL displacements for a p-polarized probe beam are obtained between −10 to 150 nm as a function of the angle of incidence on the sample. Different angles of incidence are achieved by keeping a fixed angular separation between the pump and the probe beams while rotating the sample about the axis perpendicular to the plane of incidence. In another experiment, an optically thin (500 nm thick) GaAs sample allows one to use Pauli-blocking as an optical interaction to investigate the polarization and angular dependence of the SHEL in the probe beam. For such a polarization-dependent imaging technique, the SHEL displacement in the pump beam also contributes to the measured signal and is evaluated experimentally. A probe beam at normal incidence is used to measure a SHEL displacement of ∼180 nm in a transmitted p-polarized pump beam impinging on the sample with an angle of incidence of 55 degrees. Finally, two-photon absorption is used to resolve the SHEL in a (001) oriented 500 μm thick GaAs wafer using an optical source generating sub-bandgap radiation (λ = 1550 nm) with a pulse duration of 120 fs. Linearly p- and s- co-polarized pump and probe beams are also used to investigate the polarization dependence of the SHEL. All the experimental results obtained using these different optical interactions agree with the theory within the experimental error. Finally, analytical expressions of the shifts experienced by the circular components of a beam impinging at an interface between two optical media are also derived for an incident beam with an arbitrary spatial distribution.

Two colour pumping was used to investigate the short-pulse technique of Multifrequency Raman Generation (MRG) in the transient regime of Raman scattering. In the course of this study we have demonstrated the ability to generate over thirty Raman orders spanning from the infrared to the ultraviolet, investigated the dependence of this generation on the pump intensities and the dispersion characteristics of the hollow-fibre system in which the experiment was conducted, and developed a simple computer model to help understand the exhibited behaviours. These dependence studies have revealed some characteristics that have been previously mentioned in the literature, such as the competition between MRG and self-phase modulation, but have also demonstrated behaviours that are dramatically different than anything reported on the subject. Furthermore, through a simple modification of the experimental apparatus we have demonstrated the ability to scatter a probe pulse into many Raman orders, generating bandwidth comparable to the best pump-probe experiments of MRG. By using a numeric fast Fourier transform, we predict that our spectra can generate pulses as short as 3. 3fs, with energies an order of magnitude larger than pulses of comparable duration that are made using current techniques.

Two colour pumping was used to investigate the short-pulse technique of Multifrequency Raman Generation (MRG) in the transient regime of Raman scattering. In the course of this study we have demonstrated the ability to generate over thirty Raman orders spanning from the infrared to the ultraviolet, investigated the dependence of this generation on the pump intensities and the dispersion characteristics of the hollow-fibre system in which the experiment was conducted, and developed a simple computer model to help understand the exhibited behaviours. These dependence studies have revealed some characteristics that have been previously mentioned in the literature, such as the competition between MRG and self-phase modulation, but have also demonstrated behaviours that are dramatically different than anything reported on the subject. Furthermore, through a simple modification of the experimental apparatus we have demonstrated the ability to scatter a probe pulse into many Raman orders, generating bandwidth comparable to the best pump-probe experiments of MRG. By using a numeric fast Fourier transform, we predict that our spectra can generate pulses as short as 3. 3fs, with energies an order of magnitude larger than pulses of comparable duration that are made using current techniques.

<p>Collective behavior in many-body systems, where the dynamics of an individual element depend on the state of the entire ensemble, play an important role in both basic science research and applied technologies. Over the last twenty years, studies of such effects in cold atomic vapors have lead to breakthroughs in areas such as quantum information science and atomic and condensed matter physics. Nevertheless, in order to generate photon-mediated atom-atom coupling strengths that are large enough to produce collective behavior, these studies employ techniques that intrinsically limit their applicability. In this thesis, I describe a novel nonlinear optical process that enables me to overcome these limitations and realize a new regime of collective light-matter interaction.</p><p>My experiment involves an anisotropic cloud of cold rubidium atoms illuminated by a pair of counterpropagating optical (pump) fields propagating at an angle to the trap's long axis. When the pump beam intensities exceed a threshold value, a collective instability occurs in which new beams of light are generated spontaneously and counterpropagate along the trap's long axis. In order to understand the physical mechanism responsible for this behavior, I study first the system's nonlinear optical response when driven below the instability threshold. I find that the incident optical fields produce an optical lattice that causes the atoms to become spatially organized on the sub-wavelength length scale. This organization corresponds to the formation of an atomic density grating, which effectively couples the involved fields to one another and enables the transfer of energy between them. The loading of atoms into this grating is enhanced by my choice of field polarizations, which simultaneously results in cooling of the atoms from T~30 &mu;K to T~3 &mu;K via the Sisyphus effect. As a result, I observe a fifth-order nonlinear susceptibility &chi;^{(5)}=1.9x10^-12 (m/V)^4 that is 7 orders of magnitude larger than previously observed. In addition, because of the unique scaling of the resulting nonlinear response with material parameters, the magnitude of the nonlinearity can be large for small pump intensities (\ie, below the resonant electronic saturation intensity 1.6 mW/cm^2) while simultaneously suffering little linear absorption. I confirm my interpretation of the nonlinearity by developing a theoretical model that agrees quantitatively with my experimental observations with no free parameters.</p><p>The collective instability therefore corresponds to the situation where the cold vapor transitions spontaneously from a spatially-homogeneous state to an ordered one. This emergent organization leads to the simultaneous emission of new optical fields in a process that one can interpret either in terms of mirrorless parametric self-oscillation or superradiance. By mapping out the phase diagram for this transition, I find that the instability can occur for pump intensities as low as 1 mW/cm^2, which is approximately 50 times smaller than previous observations of similar phenomena. The intensity of the emitted light can be up to 20% of the pump beam intensity and depends superlinearly on the number of atoms, which is a clear signature of collective behavior. In addition, the generated light demonstrates temporal correlations between the counterpropagating modes of up to 0.987 and is nearly coherent over several hundred &mu;s. The most significant attributes of the light, though, are that it consists of multiple transverse spatial modes and persists in steady-state. This result represents the first observation of such dynamics, which have been shown theoretically to lead to a rich array of new phenomena and possible applications.</p> / Dissertation

The past decades have witnessed the development of new materials with large nonlinear optical properties, which have made them attractive candidats for a broad spectrum of breakthrough applications in the electro-optic and photonic fields (e.g., telecommunication and computing). A deeper understanding of the relationship between, on the one hand, the chemical structure and, on the other hand, the electronic and (linear and nonlinear) optical properties has proven useful for the rational design of new efficient materials. Reaching such an understanding has attracted major interest in the scientific community worldwide in both academia and industry. Therefore, the development of new efficient NLO chromophores and materials along with commercial devices of high quality is helped via the establishment of multidisciplinary research teams combining: (i) the theoretical modeling using quantum-chemical computational calculations; (ii) the organic synthesis; (iii) the optical characterization; and (iv) the device fabrication. In this dissertation, quantum-chemistry is used to evaluate the second- and third-order NLO properties of series of new chromophores and take advantage of a feedback loop with the experimental team to understand the structure-property relationships.