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Magister Scientiae - MSc (Chemistry) / Drinking water with high concentrations of inorganic and organic contaminants can cause adverse health defects. Specifically methyl orange dye is an organic water contaminant that has been known (along with others like methyl blue etc.) to have an increase in our water systems over the past few years due to increasing demand in industrial processes. It is therefore of utmost importance to remediate organic contaminants and ultimately enable prevention. The contaminants can be removed by photocatalysis. Anatase TiO2 is known for its photocatalytic degradation of environmental pollutants and photoelectro-chemical conversion of solar energy. However its application is limited since it is a wide band gap semiconductor, (Eg = 3.2 eV). The following study deals with the enhancement of the photocatalytic properties of TiO2 for remediation of organic water contaminants.

I used ab initio molecular dynamics calculations to model cadmium sulfide nanoparticles. The nanoparticles were originaly spherical, bulk-like zinc-blende structures. Constant temperature molecular dynamics calculations reveals that CdS nanoparticles that are about 2 nm in diameter and have unpassivated surfaces are in an amorphous structure with short range order. The nearest neighbor distance on the surface of the nanoparticles being near the wurtzite nearest neighbor distance. I wrote the program xyzSTATS and used its results in justifying the amorphous nanoparticles claim. I also estimated the band gap of the CdS nanoparticles with unpassivated dangling bonds.

In this research, the transport properties of ZnO were studied through the use of electron and neutron beam irradiation. Acceptor states are known to form deep in the bandgap of doped ZnO material. By subjecting doped ZnO materials to electron and neutron beams we are able to probe, identify and modify transport characteristics relating to these deep accepter states. The impact of irradiation and temperature on minority carrier diffusion length and lifetime were monitored through the use of the Electron Beam Induced Current (EBIC) method and Cathodoluminescence (CL) spectroscopy. The minority carrier diffusion length, L, was shown to increase as it was subjected to increasing temperature as well as continuous electron irradiation. The near-band-edge (NBE) intensity in CL measurements was found to decay as a function of temperature and electron irradiation due to an increase in carrier lifetime. Electron injection through application of a forward bias also resulted in a similar increase of minority carrier diffusion length. Thermal and electron irradiation dependences were used to determine activation energies for the irradiation induced effects. This helps to further our understanding of the electron injection mechanism as well as to identify possible defects responsible for the observed effects. Thermal activation energies likely represent carrier delocalization energy and are related to the increase of diffusion length due to the reduction in recombination efficiency. The effect of electron irradiation on the minority carrier diffusion length and lifetime can be attributed to the trapping of non-equilibrium electrons on neutral acceptor levels. The effect of neutron irradiation on CL intensity can be attributed to an increase in shallow donor concentration. Thermal activation energies resulting from an increase in L or decay of CL intensity monitored through EBIC and CL measurements for p-type Sb doped ZnO were found to be the range of Ea = 112 to 145 meV. P-type Sb doped ZnO nanowires under the influence of temperature and electron injection either through continuous beam impacting or through forward bias, displayed an increase in L and corresponding decay of CL intensity when observed by EBIC or CL measurements. These measurements led to activation energies for the effect ranging from Ea = 217 to 233 meV. These values indicate the possible involvement of a SbZn-2VZn acceptor complex. For N-type unintentionally doped ZnO, CL measurements under the influence of temperature and electron irradiation by continuous beam impacting led to a decrease in CL intensity which resulted in an electron irradiation activation energy of approximately Ea = 259 meV. This value came close to the defect energy level of the zinc interstitial. CL measurements of neutron irradiated ZnO nanostructures revealed that intensity is redistributed in favor of the NBE transition indicating an increase of shallow donor concentration. With annealing contributing to the improvement of crystallinity, a decrease can be seen in the CL intensity due to the increase in majority carrier lifetime. Low energy emission seen from CL spectra can be due to oxygen vacancies and as an indicator of radiation defects.

Polymeric materials are attractive candidates for the fabrication of low cost, large area photovoltaic devices. Controlling the band gap of the electroactive polymer is an essential factor in optimizing the resulting devices. In this dissertation, a methodology for the synthesis of well-defined semiconducting materials with tunable band gaps is described. First, the synthesis, characterization, and computational analysis of a variety of trimers consisting of two 3-hexylthiophene units flanking a central moiety consisting of thiophene, or one of the electron donating monomers isothianaphthene or thieno[3,4,b]thiophene will be described. From this analysis the influences of the electronic and steric structure of the materials will be investigated. Several of these trimers will then be used in the synthesis of well-defined, higher order, oligomers of thiophene and isothianaphthene in varying compositions. Polymerization of these oligomers yields polymers of known sequence allowing the band gap of the polymers to be systematically varied. Finally, preliminary investigations into the development of alternate oligomer core units will be described. The control over the band gap that this method affords will be useful in the optimization of polymeric semiconductor devices.

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