Growth and characterization of III-V compound semiconductor nanostructures by metalorganic chemical vapor deposition

Planar <110> GaAs nanowires and quantum dots grown by atmospheric MOCVD have been introduced to non-standard growth conditions such as incorporating Zn and growing them on free-standing suspended films and on 10° off-cut substrates. Zn doped nanowires exhibited periodic notching along the axis of the wire that is dependent on Zn/Ga gas phase molar ratios. Planar nanowires grown on suspended thin films give insight into the mobility of the seed particle and change in growth direction. Nanowires that were grown on the off-cut sample exhibit anti-parallel growth direction changes. Quantum dots are grown on suspended thin films and show preferential growth at certain temperatures. Envisioned nanowire applications include twin-plane superlattices, axial pn-junctions, nanowire lasers, and the modulation of nanowire growth direction against an impeding barrier and varying substrate conditions.

Quantitative characterization of physico-chemical properties of the active layers of reverse osmosis and nanofiltration membranes, and their relation to membrane performance

The main objectives of this dissertation were: (i) to develop experimental and analytical procedures to quantify different physico-chemical properties of the ultra-thin (~ 100 nm) active layers of reverse osmosis (RO) and nanofiltration (NF) membranes and their interactions with contaminants; (ii) to use such procedures to evaluate the similarities and differences between the active layers of different RO/NF membranes; and (iii) to relate characterization results to membrane performance. Such objectives were motivated by the current limited understanding of the physico-chemical properties of active layers as a result of traditional characterization techniques having limitations associated with the nanometer-scale spatial resolution required to study these ultra-thin films. Functional groups were chosen as the main active layer property of interest. Specific accomplishments of this study include the development of procedures to quantify in active layers as a function of pH: (1) the concentration of both negatively and positively ionized functional groups; (2) the stoichiometry of association between ions (i.e., barium) and ionized functional groups (i.e., carboxylate and sulfonate); and (3) the steric effects experienced by ions (i.e., barium). Conceptual and mathematical models were developed to describe experimental results. The depth heterogeneity of the active layer physico-chemical properties and interactions with contaminants studied in this dissertation was also characterized. Additionally, measured concentrations of ionized functional groups in the polyamide active layers of several commercial RO/NF membranes were used as input in a simplified RO/NF transport model to predict the rejection of a strong electrolyte (i.e., potassium iodide) and a weak acid (i.e., arsenious acid) at different pH values based on rejection results at one pH condition. The good agreement between predicted and experimental results showed that the characterization procedures developed in this study serve as useful tools in the advancement of the understanding of the properties and structure of the active layers of RO/NF membranes, and the mechanisms of contaminant transport through them.

Identification and characterization of shallow impurity states in gallium arsenide and indium phosphide using photothermal ionization spectroscopy

A model of far infrared (FIR) dielectric response of shallow impurity states in a semiconductor has been developed and is presented for the specific case of the shallow donor transitions in high purity epitaxial GaAs. The model is quite general, however, and should be applicable with slight modification, not only to shallow donors in other materials such as InP, but also to shallow acceptors and excitons. The effects of the enormous dielectric response of shallow donors on the FIR optical properties of reflectance, transmittance, and absorptance, and photoconductive response of high purity epitaxial GaAs films are predicted and compared with experimental photothermal ionization spectra. The model accounts for many of the peculiar features that are frequently observed in these spectra, one of which was the cause of erroneous donor identifications in the early doping experiments. The model also corrects some commonly held misconceptions concerning photo-thermal ionization peak widths and amplitudes and their relationships to donor and acceptor concentrations. These corrections are of particular relevance to the proper interpretation of photothermal ionization spectra in the study of impurity incorporation in high purity epitaxial material. The model also suggests that the technique of FIR reflectance, although it has not been widely employed, should be useful in the study of shallow impurities in semiconductors.