Solar hydrogen has the potential to replace fossil fuels with a sustainable energy carrier that can be produced from sunlight and water via &quotewater splitting&quote. This study investigates the use of hematite (Fe&sub2O&sub3) as a photoelectrode for photoelectrochemical water splitting. Fe&sub2O&sub3 has a narrow indirect band-gap, which allows the utilization of a substantial fraction of the solar spectrum. However, the water splitting efficiencies for Fe&sub2O&sub3 are still low due to poor absorption characteristics, and large losses due to recombination in the bulk and at the surface. The thesis investigates the use of nanostructured composite electrodes, where thin films of Fe&sub2O&sub3 are deposited onto a nanostructured metal oxide substrate, in order to overcome some of the factors that limit the water splitting efficiency of Fe&sub2O&sub3. Doped (Si, Ti) and undoped Fe&sub2O&sub3 thin films were prepared using vacuum deposition techniques, and their photoelectrochemical, electrical, optical and structural properties were characterised. The doped Fe&sub2O&sub3 exhibited much higher photoelectrochemical activity than the undoped material, due to an improvement of the surface transfer coefficient and some grain boundary passivation. Schottky barrier modeling of Fe&sub2O&sub3 thin films showed that either the width of the depletion region or the diffusion length is the dominant parameter with a value around 30 nm, and confirmed that the surface charge transfer coefficient is small. An extensive review of the conduction mechanisms of Fe&sub2O&sub3 is presented. ZnO and SnO&sub2 nanostructures were investigated as substrates for the Fe&sub2O&sub3 thin films. Arrays of well-aligned high aspect ratio ZnO nanowires were optimised via the use of nucleation seeds and by restricting the lateral growth of the nanostructures. The geometry of the nanostructured composite electrodes was designed to maximise absorption and charge transfer processes. Composite nanostructured electrodes showed lower quantum efficiencies than equivalent thin films of Fe&sub2O&sub3, though a relative enhancement ofcollection of long wavelength charge carriers was observed, indicating that the nanostructured composite electrode concept is worthy of further investigation. The rate-limiting step for water splitting with Fe&sub2O&sub3 is not yet well understood and further investigations of the surface and bulk charge transfer properties are required in order to design electrodes to overcome specific shortcomings.

[Truncated abstract] In this dissertation an investigation into the utility of mechanochemically synthesized nanopowders for intermediate temperature solid oxide fuel cell components is reported. The results are presented in the following parts: the synthesis and characterisation of precursors for ceramic and cermet components for the fuel cell; the physical and electrical characterisation of the electrolyte and electrodes; and the fabrication, operation and analysis of the resulting fuel cells. Samarium-doped (20 mol%) ceria (SDC) nanopowder was fabricated by the solid-state mechanochemical reaction between SmCl3 with NaOH and Ce(OH)4 in 85 vol% dilution with NaCl. A milling time of 4 hours and heat treatment for 2 hours at 700°C yielded a material with equivalent particle and crystallite sizes of 17 nm. The existence of a complete solid solution was affirmed by electron energy loss spectroscopy and x-ray diffraction analysis. Doped-ceria compacts were sintered for 4 hours at 1350°C forming ceramics of 88% theoretical density. The ionic conductivity in flowing air was 0.009 S/cm, superior to commercially supplied nanoscale SDC. Anode precursor composite NiO-SDC nanopowder was synthesized by milling Ni(OH)2 with the previously defined SDC formulation ... Anode-supported fuel cells were fabricated on a substrate of at least 500 'm 55wt%NiO-SDC with 17vol% graphite pore formers. Suspensions of SDC were deposited by aerosol on the sintered bilayer at a thickness around 5 'm. A cathode of 10% SDC (SmSr)0.5CoO3 was deposited onto the sintered electrolyte and after firing had a thickness of around 25 'm. Operation of fuel cells in single-chamber mixtures of CH4 and air diluted in argon were successful and gave power outputs of 483 'W/cm2. Operation in undiluted 25 vol% CH4:air gave a power output of 5.5 mW/cm2. It was shown that a large polarisation resistance of 4.1 Ω.cm2 existed and this was assigned to losses in the anode, namely mass transport limitation associated with the catalytic combustion of methane and insufficient porosity. The large surface area of Ni appeared to allow more methane to combust and hence prevented its electrochemical reaction from occurring, thus limiting the performance of the cell. The synthesis procedures, ceramic processing and fabrication techniques and testing methods are discussed and contribute significant understanding to the fields of ceramic science and fuel cell technology.

We report on the characteristics of a ZnO based metal insulator semiconductor (MIS) diode comprised of a heterostructure of n-ZnO nanorods/n-GaN. The MIS structure consisted of unintentional - doped n type ZnO nanorods grown on n-GaN sample using hydrothermal synthesis at low temperature (100°). The ZnO nanorod layer was vertically grown from the GaN sample, having the diameter 100nm and length 2µm. Then, an insulator layer for electrical isolation was deposited on the top of ZnO nanorod layer by using spin coating method. A metal layer (gold) was finally deposited on the top. The I-V dependences show a rectifying diode like behavior with a leakage current of 2.10⁻⁵ A and a threshold voltage of about 3V. Depend on the thickness of the insulator, the I-V dependences of the n-ZnO/n-GaN heterostructure was varied from rectifying behavior to Ohmic and nearly linear. / Singapore-MIT Alliance (SMA)

Nanozirconia ceramics have great potential to be used in a range of applications from dental implants to petrochemical valves due to their enhanced mechanical properties and superior hydrothermal ageing resistance. Unlike conventional ceramic components that are normally produced in large quantities with low costs using various conventional dry forming or wet forming methods, industry scale processing of nanoceramics has not yet been achieved. Concentration and granulation of nanostructured 3 mol% yttria stabilised zirconia via a spray freeze drying (SFD) technique was investigated to determine whether large scale dry forming of nanoceramics would be possible. Commercial nanosuspension with a primary particle size of 16 nm was concentrated to 55 wt% solids content using an electrosteric dispersant, β-alanine, whilst retaining low viscosities of ~20 mPa s at a 200 s-1 shear rate. The nanosuspensions concentrated using the β-alanine also displayed good ageing resistance and it has been proven that a large scale vacuum assisted rotary evaporator can be used to perform concentration in industry.

abstract: A primary motivation of research in photovoltaic technology is to obtain higher efficiency photovoltaic devices at reduced cost of production so that solar electricity can be cost competitive. The majority of photovoltaic technologies are based on p-n junction, with efficiency potential being much lower than the thermodynamic limits of individual technologies and thereby providing substantial scope for further improvements in efficiency. The thesis explores photovoltaic devices using new physical processes that rely on thin layers and are capable of attaining the thermodynamic limit of photovoltaic technology. Silicon heterostructure is one of the candidate technologies in which thin films induce a minority carrier collecting junction in silicon and the devices can achieve efficiency close to the thermodynamic limits of silicon technology. The thesis proposes and experimentally establishes a new theory explaining the operation of silicon heterostructure solar cells. The theory will assist in identifying the optimum properties of thin film materials for silicon heterostructure and help in design and characterization of the devices, along with aiding in developing new devices based on this technology. The efficiency potential of silicon heterostructure is constrained by the thermodynamic limit (31%) of single junction solar cell and is considerably lower than the limit of photovoltaic conversion (~ 80 %). A further improvement in photovoltaic conversion efficiency is possible by implementing a multiple quasi-fermi level system (MQFL). A MQFL allows the absorption of sub band gap photons with current being extracted at a higher band-gap, thereby allowing to overcome the efficiency limit of single junction devices. A MQFL can be realized either by thin epitaxial layers of alternating higher and lower band gap material with nearly lattice matched (quantum well) or highly lattice mismatched (quantum dot) structure. The thesis identifies the material combination for quantum well structure and calculates the absorption coefficient of a MQFl based on quantum well. GaAsSb (barrier)/InAs(dot) was identified as a candidate material for MQFL using quantum dot. The thesis explains the growth mechanism of GaAsSb and the optimization of GaAsSb and GaAs heterointerface. / Dissertation/Thesis / Ph.D. Electrical Engineering 2011

Baddeleyite (monoclinic-ZrO2) is an exceptionally common accessory phase in many of the mafic and ultra-mafic rocks prevalent throughout the Solar System. This study presents the first ground-truthing efforts in the development of this robust mineral into a diagnostic indicator, discrete barometer, and precise U-Pb geochronometer of shock metamorphism by combining electron backscatter diffraction and atom probe tomography to generate unique chemical and structural datasets. Microstructural analysis of variably shocked baddeleyite grains around the Sudbury impact structure (Ontario, Canada) highlights a series of crystallographic structures that can be correlated with discrete variations in formative pressure-temperature conditions. Decompression at high temperatures generates a series of interlocking reversion twinned structures, while quenching forms a quasi-amorphous matrix. These features are comparable to those observed in extra-terrestrial samples, where they can be directly linked with the severity and extent of lead loss and age resetting. This finding facilitates the application of baddeleyite as a shock indicator, barometer (>5 GPa) and chronometer in a wide range of planetary materials. This structural variability is also observable on the nanometre scale. Analysis of the most highly shocked Sudbury baddeleyite using atom probe tomography reveals planar and curvi-planar fractures, trace element enriched subgrain boundaries, and solid-state diffusion clusters. These micrometre and nanometre scale features encourage localised diffusion of lead, with whole-microtip U-Pb analyses yielding complex partially reset ages. The application of atom probe tomography allows these features to be spatially resolved on the nanometre scale, yielding highly accurate ages for protolith crystallization and impact metamorphism within a single grain. These results have significant implications for the isotopic analysis of baddeleyite-bearing planetary materials, where the mechanisms of U-Pb age resetting have until now been poorly understood.

abstract: This dissertation research has involved microscopic characterization of magnetic nanostructures using off-axis electron holography and Lorentz microscopy. The nanostructures investigated have included Co nanoparticles (NPs), Au/Fe/GaAs shell/core nanowires (NWs), carbon spirals with magnetic cores, magnetic nanopillars, Ni-Zn-Co spinel ferrite and CoFe/Pd multilayers. The studies have confirmed the capability of holography to describe the behavior of magnetic structures at the nanoscale. The phase changes caused by the fringing fields of chains consisting of Co NPs were measured and calculated. The difference between chains with different numbers of Co NPs followed the trend indicated by calculations. Holography studies of Au/Fe/GaAs NWs grown on (110) GaAs substrates with rotationally non-uniform coating confirmed that Fe was present in the shell and that the shell behaved as a bar magnet. No fringing field was observed from NWs with cylindrical coating grown on (111)B GaAs substrates. The most likely explanation is that magnetic fields are confined within the shells and form closed loops. The multiple-magnetic-domain structure of iron carbide cores in carbon spirals was imaged using phase maps of the fringing fields. The strength and range of this fringing field was insufficient for manipulating the carbon spirals with an external applied magnetic field. No magnetism was revealed for CoPd/Fe/CoPd magnetic nanopillars. Degaussing and MFM scans ruled out the possibility that saturated magnetization and sample preparation had degraded the anisotropy, and the magnetism, respectively. The results suggested that these nanopillars were not suitable as candidates for prototypical bit information storage devices. Observations of Ni-Zn-Co spinel ferrite thin films in plan-view geometry indicated a multigrain magnetic domain structure and the magnetic fields were oriented in-plane only with no preferred magnetization distribution. This domain structure helps explain this ferrite's high permeability at high resonance frequency, which is an unusual character. Perpendicular magnetic anisotropy (PMA) of CoFe/Pd multilayers was revealed using holography. Detailed microscopic characterization showed structural factors such as layer waviness and interdiffusion that could contribute to degradation of the PMA. However, these factors are overwhelmed by the dominant effect of the CoFe layer thickness, and can be ignored when considering magnetic domain structure. / Dissertation/Thesis / Doctoral Dissertation Engineering 2015

abstract: Zinc telluride (ZnTe) is an attractive II-VI compound semiconductor with a direct bandgap of 2.26 eV that is used in many applications in optoelectronic devices. Compared to the two dimensional (2D) thin-film semiconductors, one-dimensional (1D) nanowires can have different electronic properties for potential novel applications. In this work, we present the study of ZnTe nanowires (NWs) that are synthesized through a simple vapor-liquid-solid (VLS) method. By controlling the presence or the absence of Au catalysts and controlling the growth parameters such as growth temperature, various growth morphologies of ZnTe, such as thin films and nanowires can be obtained. The characterization of the ZnTe nanostructures and films was performed using scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDX), high- resolution transmission electron microscope (HRTEM), X-ray diffraction (XRD), photoluminescence (PL), Raman spectroscopy and light scattering measurement. After confirming the crystal purity of ZnTe, two-terminal diodes and three-terminal transistors were fabricated with both nanowire and planar nano-sheet configurations, in order to correlate the nanostructure geometry to device performance including field effect mobility, Schottky barrier characteristics, and turn-on characteristics. Additionally, optoelectronic properties such as photoconductive gain and responsivity were compared against morphology. Finally, ZnTe was explored in conjunction with ZnO in order to form type-II band alignment in a core-shell nanostructure. Various characterization techniques including scanning electron microscopy, energy-dispersive X-ray spectroscopy , x-ray diffraction, Raman spectroscopy, UV-vis reflectance spectra and photoluminescence were used to investigate the modification of ZnO/ZnTe core/shell structure properties. In PL spectra, the eliminated PL intensity of ZnO wires is primarily attributed to the efficient charge transfer process occurring between ZnO and ZnTe, due to the band alignment in the core/shell structure. Moreover, the result of UV-vis reflectance spectra corresponds to the band gap energy of ZnO and ZnTe, respectively, which confirm that the sample consists of ZnO/ZnTe core/shell structure of good quality. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2017

abstract: The properties of adjuvants to stimulate an immune response to treat cancer has sparked a major area of research in the field of immunotherapy. Given the presence of multiple RNA sensors in mammalian host cells for eliciting innate immunity, synthetic RNA nanostructures present a unique opportunity for adjuvant exploration. While RNA nanostructures are organic and biocompatible in nature than other adjuvants, they could be tailored to have desired structural stability and functional diversity for in vivo application. In this study, a rectangular RNA origami nanostructure was designed to contain double-stranded RNA motifs and possess high structural stability. Using in vitro assays, RNA origami was shown to stimulate the toll-like receptor 3 (TLR3) signaling pathway, which has been reported to activate antigen presenting cells (APCs), natural killer (NK) cells, cluster of differentiation 8 (CD8) T-cells, and the secretion of proinflammatory cytokines. To explore RNA origami as an adjuvant for cancer immunotherapy, intraperitoneal administration of a murine colon cancer cell line (CT26) was used as a model system to mimic peritoneal metastasis (PM), in which RNA origami was investigated for its activities in mitigating PM tumor microenvironment and improving anti-tumor immunity. Given the poor outcome of the patients with PM and urgent need for new interventions, this study aims to translate the adjuvant activities of RNA origami demonstrated in vitro into potent anti-cancer immunotherapeutics. Here, it was shown that multiple intraperitoneal injections of RNA origami could inhibit tumor growth, leading to a significant delay and/or regression of metastatic tumor growth in the peritoneum. Furthermore, tumor-free mice, after being treated with RNA origami, were also resistant to a second challenge of tumor cells, indicating the development of the adaptive anti-tumor immunity. This immunity is dependent on T-cells since nude mice succumbed to tumor growth with or without RNA origami treatment. Thus, RNA-origami can function as an adjuvant to activate the innate immunity and subsequently the adaptive anti-tumor immunity, leading to tumor regression. Conceivably, RNA origami could be explored as an immunotherapeutic agent to improve the disease outcome of patients with peritoneal metastasis and peritoneal carcinogenesis. / Dissertation/Thesis / Masters Thesis Molecular and Cellular Biology 2018

abstract: The discovery of DNA helical structure opened the door of modern molecular biology. Ned Seeman utilized DNA as building block to construct different nanoscale materials, and introduced a new field, know as DNA nanotechnology. After several decades of development, different DNA structures had been created, with different dimension, different morphology and even with complex curvatures. In addition, after construction of enough amounts DNA structure candidates, DNA structure template, with excellent spatial addressability, had been used to direct the assembly of different nanomaterials, including nanoparticles and proteins, to produce different functional nanomaterials. However there are still many challenges to fabricate functional DNA nanostructures. The first difficulty is that the present finite sized template dimension is still very small, usually smaller than 100nm, which will limit the application for large amount of nanomaterials assembly or large sized nanomaterials assembly. Here we tried to solve this problem through developing a new method, superorigami, to construct finite sized DNA structure with much larger dimension, which can be as large as 500nm. The second problem will be explored the ability of DNA structure to assemble inorganic nanomaterials for novel photonic or electronic properties. Here we tried to utilize DNA Origami method to assemble AuNPs with controlled 3D spacial position for possible chiral photonic complex. We also tried to assemble SWNT with discrete length for possible field effect transistor device. In addition, we tried to mimic in vivo compartment with DNA structure to study internalized enzyme behavior. From our results, constructed DNA cage origami can protect encapsulated enzyme from degradation, and internalized enzyme activity can be boosted for up to 10 folds. In summary, DNA structure can serve as an ideal template for construction of functional nanomaterials with lots of possibilities to be explored. / Dissertation/Thesis / Ph.D. Chemistry 2013