Diamond-like semiconductors are interesting materials to study due to the wide variety of technologically useful properties that these materials possess. These normal valence compounds have structures that are based on that of diamond, either the cubic or hexagonal polymorph. Though there are a finite number of possible compounds, due to isovalent and isoelectronic principles, the total number of potential compounds is quite extensive. Quaternary diamond-like semiconductors provide a unique opportunity, because much of the previous research has focused on binary and ternary systems leaving quaternary systems, relatively unexplored. Additionally, quaternary diamond-like semiconductors possess a greater degree of compositional flexibility compared to binary and ternary materials, which could result in the ability to more carefully tune desired physical properties. <br>In order to prepare the new materials, Li2ZnGeS4, Li2ZnSnS4, Li2CdGeS4, Li2CdSnS4 and Ag2MnSnS4, several synthetic methods have been employed, including high-temperature solid-state synthesis, polychalcogenide flux synthesis and solid-state microwave synthesis. The solid-state microwave synthetic method was itself studied using a number of target systems such as the ternary diamond-like semiconductor, AgInSe2. Additionally, several intermetallic compounds, such as Ag3In, AuIn2 and Bi2Pd were prepared using this procedure. Solid-state microwave synthesis is not as well known as some of the other synthetic methods that were employed in this work possibly due to a lack of understanding of the method, training and equipment. Despite these problems, the method has the potential to save time, energy and cost due to the unique nature of microwave heating. In an attempt to gain a better understanding of this synthetic method and its capabilities, the solid-state microwave synthetic method was used to prepare diamond-like semiconductors and intermetallic compounds. / Bayer School of Natural and Environmental Sciences / Chemistry and Biochemistry / PhD / Dissertation

High Harmonic Generation (HHG) enables the production of bursts of coherent soft x-rays with attosecond pulse duration. This process arrises from the nonlinear interaction between intense infrared laser pulses and an ionizing gas medium. Soft x-ray photons are used for spectroscopy of inner-shell electron correlation and exchange processes, and the availability of attosecond pulse durations will enable these processes to be resolved on their natural time scales. The maximum or cutoff photon energy in HHG increases with both the intensity as well as the wavelength of the driving laser. It is highly desirable to increase the harmonic cutoff as this will allow for the generation of shorter attosecond pulses, as well as HHG spectroscopy of increasingly energetic electronic transitions. While the harmonic cutoff increases with laser wavelength, there is a corresponding decrease in harmonic yield. The first part of this thesis describes the experimental measurement of the wavelength scaling of HHG efficiency, which we report as lambda^(-6.3) in xenon, and lambda^(-6.5) in krypton. To increase the HHG cutoff, we have developed a 1.8 um source, with stable carrier envelope phase and a pulse duration of <2 optical cycles. The 1.8 um wavelength allowed for a significant increase in the harmonic cutoff compared to equivalent 800 nm sources, while still maintaing reasonable harmonic yield. By focusing this source into neon we have produced 400 eV harmonics that extend into the x-ray water window. In addition to providing a source of photons for a secondary target, the HHG spectrum caries the signature of the electronic structure of the generating medium. In krypton we observed a Cooper minimum at 85 eV, showing that photoionization cross sections can be measured with HHG. Measurements in xenon lead to the first clear observation of electron correlation effects during HHG, which manifest as a broad peak in the HHG spectrum centred at 100 eV. This thesis also describes several improvements to the HHG experiment including the development of an ionization detector for measuring laser intensity, as well as an investigation into the role of laser mode quality on HHG phase matching and efficiency.

Abstract: Nonlinear multicontrast microscopy is established in this study as an important tool for understanding biological structure and function of muscle cells. Second harmonic generation, third harmonic generation and multi-photon excitation fluorescence are acquired simultaneously in order to establish the origin of nonlinear signal generation in myocytes, and investigate myocyte structure and functionality during muscle contraction. Using structural cross-correlation image analysis, an algorithm developed specifically for this research, for the first time, third harmonic generation is shown to originate from the mitochondria in myocytes. The second harmonic, which is generated from the anisotropic bands of the sarcomeres, is further shown to be dependent on the crystalline order of the sarcomeres, thereby providing a potential diagnostic tool to evaluate disorder in muscle cells. The combination of the second and third harmonic provides complementary information that can be used to further elucidate the basic principles of muscle contraction. Time-lapse nonlinear microscopic imaging showed structural and functional dynamics in the myocytes. The second harmonic contrast revealed nonsynchronized nanocontractions of sarcomeres in relaxed, non-contracting, cardiomyocytes and Drosophila muscle samples, providing insight into the asynchronous behaviour of individual sarcomeres. Furthermore, macrocontracting samples were found to exhibit a synchronization of nanocontractions, providing new evidence for how muscles contract. Dynamic image correlation analysis, another algorithm developed specifically for this investigation, is used to reveal networks of mitochondria, which show fluctuations of multi-photon excitation fluorescence and third harmonic generation signals. The intensity fluctuations in the networks reveal both slow and fast dynamics; phase shifts of the slow dynamics between different networks are observed. Fast dynamics appear only in the inner networks, suggesting functional difference between interfibrillar and subsarcolemma mitochondria. The groundwork for studying bioenergetics of mitochondria in cardiomyocytes with nonlinear multimodal microscopy is fully developed in this work. The origin of the nonlinear signals and the development of the image analysis techniques provide a solid foundation to further study of muscle contractility and bioenergetics.

Conventional step-index silica fibers do not possess a second-order optical nonlinearity due to symmetry concerns. However, through the process of poling, the generation of a frozen-in DC field $E^{DC}$, and in turn, a non-zero second-order nonlinearity $\chi^{(2)} = 3\chi^{(3)}E^{DC}$, can be created in optical fibers. In this thesis, I measure the individual $\chi^{(2)}$ tensor elements of birefringent periodically poled fiber via second-harmonic generation and sum-frequency generation experiments. The symmetry of the $\chi^{(2)}$ tensor is consistent with that of the $\chi^{(3)}$ for isotropic media. This is the first study that characterizes all the $\chi^{(2)}$ tensor elements in birefringent poled fiber. Furthermore, I investigate the intermix of the $\chi^{(2)}$ tensor elements by twisting the fiber, which results in the generation of new second-harmonic signals not observed in untwisted fiber. The conversion efficiencies and spectral positions of these new signals can be varied by twisting the fiber.

The three wave mixing process was modeled in GaAs:AlGaAs superlattices using two new modeling tools that were developed in the course of this work: A 2D beam propagation tool for optimizing quasi-phase matching gratings, and a 1D iterative beam propagation tool for determining the output powers and threshold of optical parametric oscillators of arbitrary geometries. The 2D tool predicts close to 80% enhancement of conversion e ciency by phase matching near 800 nm compared to 775 nm, which was the originally designed operation wavelength. The model also predicts resonant behaviour for an abrupt grating pro le. The 1D tool was used to determine the threshold conditions for para- metric oscillation for di erent geometries. The performances of di erent phase matching approaches in AlGaAs were quantitatively compared. The model also indicated the need for pulsed operation to achieve reasonably low threshold powers in AlGaAs waveguides.

Conventional step-index silica fibers do not possess a second-order optical nonlinearity due to symmetry concerns. However, through the process of poling, the generation of a frozen-in DC field $E^{DC}$, and in turn, a non-zero second-order nonlinearity $\chi^{(2)} = 3\chi^{(3)}E^{DC}$, can be created in optical fibers. In this thesis, I measure the individual $\chi^{(2)}$ tensor elements of birefringent periodically poled fiber via second-harmonic generation and sum-frequency generation experiments. The symmetry of the $\chi^{(2)}$ tensor is consistent with that of the $\chi^{(3)}$ for isotropic media. This is the first study that characterizes all the $\chi^{(2)}$ tensor elements in birefringent poled fiber. Furthermore, I investigate the intermix of the $\chi^{(2)}$ tensor elements by twisting the fiber, which results in the generation of new second-harmonic signals not observed in untwisted fiber. The conversion efficiencies and spectral positions of these new signals can be varied by twisting the fiber.

The three wave mixing process was modeled in GaAs:AlGaAs superlattices using two new modeling tools that were developed in the course of this work: A 2D beam propagation tool for optimizing quasi-phase matching gratings, and a 1D iterative beam propagation tool for determining the output powers and threshold of optical parametric oscillators of arbitrary geometries. The 2D tool predicts close to 80% enhancement of conversion e ciency by phase matching near 800 nm compared to 775 nm, which was the originally designed operation wavelength. The model also predicts resonant behaviour for an abrupt grating pro le. The 1D tool was used to determine the threshold conditions for para- metric oscillation for di erent geometries. The performances of di erent phase matching approaches in AlGaAs were quantitatively compared. The model also indicated the need for pulsed operation to achieve reasonably low threshold powers in AlGaAs waveguides.

Abstract: Nonlinear multicontrast microscopy is established in this study as an important tool for understanding biological structure and function of muscle cells. Second harmonic generation, third harmonic generation and multi-photon excitation fluorescence are acquired simultaneously in order to establish the origin of nonlinear signal generation in myocytes, and investigate myocyte structure and functionality during muscle contraction. Using structural cross-correlation image analysis, an algorithm developed specifically for this research, for the first time, third harmonic generation is shown to originate from the mitochondria in myocytes. The second harmonic, which is generated from the anisotropic bands of the sarcomeres, is further shown to be dependent on the crystalline order of the sarcomeres, thereby providing a potential diagnostic tool to evaluate disorder in muscle cells. The combination of the second and third harmonic provides complementary information that can be used to further elucidate the basic principles of muscle contraction. Time-lapse nonlinear microscopic imaging showed structural and functional dynamics in the myocytes. The second harmonic contrast revealed nonsynchronized nanocontractions of sarcomeres in relaxed, non-contracting, cardiomyocytes and Drosophila muscle samples, providing insight into the asynchronous behaviour of individual sarcomeres. Furthermore, macrocontracting samples were found to exhibit a synchronization of nanocontractions, providing new evidence for how muscles contract. Dynamic image correlation analysis, another algorithm developed specifically for this investigation, is used to reveal networks of mitochondria, which show fluctuations of multi-photon excitation fluorescence and third harmonic generation signals. The intensity fluctuations in the networks reveal both slow and fast dynamics; phase shifts of the slow dynamics between different networks are observed. Fast dynamics appear only in the inner networks, suggesting functional difference between interfibrillar and subsarcolemma mitochondria. The groundwork for studying bioenergetics of mitochondria in cardiomyocytes with nonlinear multimodal microscopy is fully developed in this work. The origin of the nonlinear signals and the development of the image analysis techniques provide a solid foundation to further study of muscle contractility and bioenergetics.

Genetic algorithm is often used to find the global optimum in a multi-dimensional search problem. Inspired by the natural evolution process, this algorithm employs three reproduction strategies -- cloning, crossover and mutation -- combined with selection, to improve the population as the evolution progresses from generation to generation. Femtosecond laser pulse tailoring, with the use of a pulse shaper, has become an important technology which enables applications in femtochemistry, micromachining and surgery, nonlinear microscopy, and telecommunications. Since a particular pulse shape corresponds to a point in a highly-dimensional parameter space, genetic algorithm is a popular technique for optimal pulse shape control in femtosecond laser experiments. We use genetic algorithm to optimize third harmonic generation (THG), and investigate various pulse shaper options. We test our setup by running the experiment with varied initial conditions and study factors that affect convergence of the algorithm to the optimal pulse shape. Our next step is to use the same setup to control coherent anti-Stocks Raman scattering. The results show that the THG signal has been enhanced.

Collagen is an important structural protein in living organisms and plays an indispensable role in connecting cells and tissues, such as in musculature, bone, and ligament. The stability and conformation of collagen are, however, strongly influenced by ambient temperature and constitutes an interesting subject of study. Thermally induced conformation change of collagen has been investigated by techniques such as differential scanning calorimetry (DSC) and second harmonic generation. DSC is a powerful method in uncovered important thermal dynamics properties including phase change, enthalpy, and thermal stability of the collagen. However, due to its collective nature, no localized information can be found. For comparison, second harmonic generation, which reflects structural symmetry, can be combined with laser scanning microscopy to investigate localized variation. It has been shown in previous studies that the thermal stability of collagen is strongly influenced by the water content within collagen. For comparison, we are investigating the conformational change of collagen under a vacuum stat with second harmonic microscopy so as to isolate environmental effects, particularly those from water and oxygen. In this way, we have found the conformational change of collagen takes place at a much higher temperature and activation energy. Additionally, the high spatial resolution achieved also allows many further possibilities.