Electron transport in single lateral quantum dot (QD) and parallel lateral double quantum dot (DQD) systems is modeled using semiclassical rate equations. The Zeeman effect, in conjunction with resonant tunneling, is used to select the spin of electrons involved in transport. We show adiabatic spin pumping by periodic variation of the systems' confining parameters, namely the quantum point contacts (QPCs) dictating the boundaries of the dots, and the gate voltage applied to each dot. The limitations of adiabatic spin pumping are subsequently examined by counting the average spin pumped per cycle when frequency and interdot capacitance are adjusted.

Achieving tunability of two dimensional (2D) transition metal dichalcogenides (TMDs) functions calls for the introduction of hybrid 2D materials by means of localized interactions with zero dimensional (0D) materials. A metal-semiconductor interface, as in gold (Au) - molybdenum disulfide (MoS2), is of great interest from the standpoint of fundamental science as it constitutes an outstanding platform to investigate optical and electronic properties due to charge transfer. The applied aspects of such systems introduce new options for electronics, photovoltaics, detectors, catalysis, and biosensing. Here in this dissertation, we study the charge transfer interaction between Au nanoparticals and MoS2 flakes and its effect on Photoluminescence and electronic transport properties. The MoS2 was mechanically exfoliated from bulk single crystal. Number of layers in the flake was identified with the help of AFM and Raman Spectra. Au was deposited by physical vapor deposition method (PVD) in multiple steps to decorate MoS2 flakes. We first study the photoluminescence of pristine and Au decorated MoS2 and shows that in the presence of Au, the photoluminescence of MoS2 quenches significantly. We infer that the PL quenching can be attributed to a change in the electronic structure of the MoS2-Au system. The difference in Fermi level of a of MoS2 and Au results in a 0.4 eV energy level offset, which causes a band bending in the MoS2-Au hybrid. Upon illumination, the electrons in the excited state of MoS2 transfer to Au, leaving a hole behind, thus cause p-doping in MoS2. As electrons from MoS2 are transferred to Au, they do not decay back to their initial ground state, leading to PL quenching in the hybrid system. To study the effect of Au deposition on electronic properties of ultra-thin and multilayers MoS2 flakes, we have fabricated MoS2 FETs from (1) ultra-thin sample (2-4 MoS2 layers) and (2) multilayers samples (more than 20 layers). After each deposition of Au, we measured the electrical characteristics of FET at room temperature. We show that the threshold voltage shifts towards the positive gate voltage as we increase the thickness of Au. This shift in threshold voltage is indicative of p doping of the MoS2. We further show that the field effect mobility of MoS2 FET decrease with Au thickness. We have quantitatively estimated the charge transferring from MoS2 to Au.

Interprotein electron transfer (ET) is crucial for natural energy conversion and a fundamental reaction in the pursuit of understanding the broader problem of proteinprotein interactions and reactivity. Simplifying the complicated nature of these natural systems has driven development of biomimetic approaches. Functionalized gold nanoparticles offer simplified, tunable surfaces that can serve as a proxy to study the reactivity and dynamics of proteins. Amino-acid functionalized gold nanoparticles (Au-TX) served as a complementary partner to cytochrome c (Cyt c) and catalyzed its ET reactivity without altering the native structure. Redox mediator and EPR experiments confirmed that the redox potential and coordination environment of the heme were unaltered. Varying the functionality of Au-TX under limiting redox reagent concentrations resulted in distinct ET reactivity. These conditions reflected the collision of a small redox reagent with the Cyt c/Au-TX adduct, introducing the possibility of Cyt c/Au-TX dynamics to modulate ET. Under high ionic strength conditions, the rate enhancement ranged from 0.0870 " 1011 for Cyt c/Au-TAsp to 1.95 " 1011 M-1 s-1 for Cyt c/Au-TPhe. Au-TAsp binds to a larger surface of the front face of Cyt c than Au-TPhe, likely reducing heme access and resulting in attenuated ET reactivity.Site-directed spin-labeling characterized the dynamic interactions and motion of Cyt c with Au-TX. Several mutants of Cyt c were utilized to extract information about the different dynamics of the Cyt c/Au-TPhe and Cyt c/Au-TAsp systems. Cyt c appeared to have a highly dynamic binding interaction with the surface of Au-TPhe while binding to Au-TAsp resulted in a more rigid interface, particularly at the heme crevice. The dynamic interaction of Cyt c/Au-TX at the heme crevice could promote a gated ET mechanism between Cyt c and its redox partner. Thus, the reduced reactivity of Cyt c/Au-TAsp is likely a result of both slower global dynamics and more rigid binding near the heme crevice.

Access to clean water is essential for human health and dignity. The increasingly rapid population growth, combined with the emergence of resistant chemical compounds and more concentrated toxic residues in the effluent streams of treatment plants, point towards a decline in freshwater resources resulting in a global water crisis in the next decades. Current wastewater treatment plants rely on Advanced Oxidation Processes (AOPs) for the tertiary (or advanced) step of the treatment. Photocatalysis is one of such processes, by which semiconductors are exposed to radiation of specific wavelengths (traditionally UV) to generate Reactive Oxygen Species (ROS) that can degrade organic molecules through a chain of radical oxidation reactions. Anatase titania (TiO2) has been used for many decades as a photocatalyst. Its electronic band structure has a band gap of 3.2 eV, requiring radiation in the UV range to trigger its photocatalytic properties. One way to reduce the band gap energy and shift the absorption peak wavelength to the visible part of the spectrum (thus reducing operation costs) is by doping the photocatalyst particles with transition metal atoms. Iron (III) is a great candidate due to the placement of its conduction/valence bands within titania’s band gap, its atomic radius similar to titanium (IV) and its variety of oxidation states. However, iron-doped anatase titania synthesized by ordinary sol-gel methods shows a photodegradation efficiency that is much lower than undoped anatase. Previous studies have shown that this is caused by an inconspicuous iron oxide layer on the surface of the catalyst particle, forming a physical barrier to the mobility of charge carriers that trigger the formation of ROS radicals. Small changes to the synthesis protocol, namely slowing down the hydrolysis of the Ti precursor by lowering the solution’s pH and acid-washing the final product, have been shown to result in particles that are photoactive under visible radiation and boast an unobstructed reactive surface. In this work, the novel Fe-TiO2 photocatalyst is studied and characterized in terms of its particle size distribution, inner structure and composition using electron microscopy techniques. It is important to know the particle size profile arising from this novel synthetic method, as the presence of nanoparticles could pose a health risk whereas an abundance of oversized particles is undesirable from the perspective of chemical reaction engineering (low surface-to-volume ratio). Inner structure/composition analyses could reveal whether the iron content inside the photocatalyst segregates into iron oxides, which would hinder reaction rates by behaving as a recombination center for charge carriers. As well, gathering more information about the inner structure of the catalyst (such as degree of crystallinity) is desirable as that could help fine-tune the synthesis protocol in order to obtain optimal photocatalytic activity. The particle size distribution studies using scanning electron microscopy revealed that the catalyst samples contain a significant fraction of nanoparticles (31.55% smaller than 100 nm), even though those particles represent a very small fraction of total sample volume (0.00015%) and reactive area (0.03%). Moreover, oversized particles (bigger than 5 m) account for the biggest fraction of sample volume and reactive surface. It was suggested that the size distribution of the catalyst be shifted to intermediate particle sizes by introducing additional grinding and separation steps into the synthesis protocol. The inner structure studies were carried using a combination of scanning, transmission and scanning-transmission electron microscopy, as well as spectroscopy methods such as EDX and EELS to map composition. It was found that the original anatase lattice structure remained unchanged in terms of interplanar spacings and crystallographic orientations, indicating that the addition of iron impurities at the small concentrations used here (0.5at%) did not result in discernible changes to the lattice. The monocrystalline units of Fe-TiO2 (termed crystallites) often appear to be bound together by amorphous material. No segregation of Fe was observed inside the particles at this concentration, as shown by the apparent homogenous composition of the catalyst across crystalline and amorphous regions. The external iron oxide contamination layer observed in previous studies was theorized to form during the later steps of the sol-gel process due to the precipitation of the iron content in solution that failed to be incorporated into the TiO2 gel network. More in-depth studies must be carried to assess whether preferential segregation of iron within the catalyst could occur at higher dopant concentrations. / Graduate

Part A of two Project Reports; Part B can be found at: http://hdl.handle.net/11375/17692 / <p> A number of recently published papers have been critical of the values of CE and Cλ by the ICRU as absorbed dose conversion factors for ionization chambers used in electron or photon beams.</p> <p> This report examines the subject in light of these recent works. Presented is a review of both theoretical and experimental results published to date along with the results of experimental work carried out at this facility. The present study concentrated on the measurement of the absorbed dose conversion factors for electrons and 25 NW photons. It also attempted to determine how the conversion factors might be influenced by such factors as chamber design buildup cap thickness and composition, and phantom composition.</p> <p> Measurements were made using electrons with 10 to 32 MeV initial energy and a 25 MeV photon beam, all produced by a Sagittaire Model Therac 40 linear accelerator. Checks on the stability of the measurement system were made using a 60Co source. Fricke ferrous sulfate dosimetry was used for absorbed dose measurement in the determination of CE.</p> <p> The results of the study would indicate that there is little or no effect on the measured values of CE or Cλ introduced by either the sleeves or phantoms for the radiation qualities studied. The results of the absorbed dose conversion factor study would indicate that the values recommended by the ICRU are sufficiently accurate for use in most instances. The data would tend to support the arguement that if there is an error in one of the ICRU derivations, the error in theory lies in the CE determination rather than that for Cλ.</p> / Thesis / Master of Engineering (MEngr)

This is Part B of the Thesis. / <p> The design and performance of a flat emitting ring on-axis electron gun suitable for use in a small reflected beam accelerator was investigated. The design constraints include a low emittance (approximately 5π cm mrad), and a small beam size with a focus approximately 13 cm from the emitting surface.</p> <p> A suitable geometry was determined theoretically and was tested with a dispenser cathode. A beam with a focus at 12.7 ± 1 cm and an emittance of approximately 7π cm mrad was obtained. However, the dispenser cathode response time to heater current changes is too large for the required gun current control.</p> <p> Experiments were done to study the mechanical and thermal properties of flat emitting foil rings, since a directly heated foil has a fast response time. Two foils were tested: 1.27 x 10^-3 cm thick tungsten and 4.57 x 10^-4 cm thick tantalum. The present simple design requires impractically thin foils (≤ 0.25 microns thick) to reach emission temperatures at feasible heater currents.</p> / Thesis / Master of Engineering (MEngr)

<p> Single crystals of sodalite have been studied by means of electron paramagnetic resonance (E. P.R.) both at 0.8 cm. and 3 cm. wavelength. The existence of at least four different E. P. R. spectra was established of which one was attributed to the manganese impurity and a possible model for two other spectra is proposed. It was found that two of the observed spectra disappear upon heat treatment although the bleaching of the characteristic blue colour of sodalite crystals does not appear to be related to any of the spectra studied. </P> / Thesis / Master of Science (MSc)

<p> The major purpose of the work described in this thesis has been the development of an analytical model for the electron-beam pumped semiconductor laser system consistent with the main dynamic effects observed experimentally in the stimulated emission. The lasing mat4:!rials used in this study were single crystals of CdS, CdS1e and GaAs. The choice was made on the basis of the availability of high purity single crystals and for representation of both II-VI and III-V materials in the study. </p> <p> Generally, the light output from a pulse-excited semiconductor laser changes in both wavelength and far-field pattern as a function of time during the excitation pulse. The effects investigated divide naturally into two parts. The first part deals with the tuning of the peak output of the stimulated emission toward lower energies during the excitation pulse. The second part deals with a deviation of the far-field radiation pattern of the spatial laser mode with respect to the cavity axis and the changes of this angle with time during the pump pulse. </p> <p> In parallel with these investigations, a theoretical model of the semiconductor laser was developed. This model takes into account spatial variations in the gain and refractive index in the semiconductor material and changes in these profiles with time. The analysis, in terms of the experimental parameters, leads to a prediction of angular tuning of the far-field mode and can account for certain features of faster-than-bandgap wavelength tuning in a number of disparate laser materials. A particularly significant consequence of the model is the prediction of dramatic variations in cavity loss as a function of time. The major consequences of this effect for laser dynamics are discussed. </p> / Thesis / Doctor of Philosophy (PhD)

<p> The a-β phase transformation was studied in hydrothermally grown crystals of A1PO4 by measuring the spin-Hamiltonian parameters of Fe^3+ as a function of temperature. </p> <p> The theory of the Blume-Orbach mechanism for the zero-field splitting of s-state ions was generalized and used to calculate the D-tensor of the spin-Hamiltonian. The experimentally observed temperature variation of the spin-Hamiltonian was interpreted in terms of a temperature-dependent point-multipole model of the charge distribution in the crystal lattice. </p> <p> A similar study of the a-S phase transformation in quartz was attempted but E.P.R. measurements could only be taken up to 450°C (123°C below the transformation temperature) because of the instability of the Fe^3+ center at higher temperatures. </p> / Thesis / Doctor of Philosophy (PhD)

<p> This thesis presents the results of an attempt to study the chemical bond in terms of the three-dimensional electronic charge distribution and the force which this charge distribution exerts on the nuclei. The homonuclear diatomic molecules Li2, B2, C2, N2, O2, and F2 are discussed in terms of covalent binding while the heteronuclear diatomic molecules LiF and LiH are discussed in terms of ionic binding.</p> / Thesis / Doctor of Philosophy (PhD)