This thesis investigates lead oxides as photovoltaic materials. Vacuum deposition methods and ex-situ annealing are used to produce different stoichiometries of lead oxide. The relationship between structure and the optoelectronic properties is then investigated. Following this, a number of photovoltaic devices are prototyped and a Kelvin probe used to determine and understand the band structure of devices. Thin films of PbO produced via air annealing of thermally evaporated lead consist of a mixture of two phases, orthorhombic and tetragonal, that determine the materials properties and effectiveness as absorber layer in a Schottky device. Films of higher tetragonal content are more photoactive, showing lower series resistance. Kelvin probe reveals that with an increasing work function of the PbO with increasing duration of the annealing, the Schottky barrier between PbO and Al increases, which results in a higher VOC. This trend is inverted when the Fermi level of PbO drops below that of ITO, creating an opposing junction. Reactively sputtered PbO2 films are highly conductive degenerate semiconductors. Increasing oxygen flow rate during deposition leads to increased resistivity and decreased mobility, resulting from a decrease in grain size. Alongside this an increase in carrier concentration is observed as the material gets less ordered at higher oxygen flow rates, which results in an increase in Fermi level. Due to its high conductivity the material is not photoactive, and the high work function between -5.6 and -5.8 eV does not allow the formation of a Schottky junction or a p-n junction with the evaporated p- type PbO. Post deposition annealing of the sputtered films leads to the formation of the more resistive Pb3O4 phase. This material shows lower carrier concentration and mobility, however, work functions are similarly high. The changes induced by the heat treatment are not substantial enough to be able to create a junction between the as-deposited and the annealed material, as is revealed by Kelvin probe and Hall Effect measurements. Heterojunctions between P3HT and Pb3O4 were made to test predictions made by KP measurements. A heat treatment on P3HT improved its electronic properties and raised the Fermi level, resulting in the transformation of a diode in to a photovoltaic device and a decrease in dark current.

Properties of polymers in thin films are distinct from those in the bulk due to the significant effects of free or substrate surfaces. The presence of a free surface allows an increased mobility of polymer chains in the near surface region, therefore, a lower glass transition temperature (T_g). With this lower surface T_g, a surface-specific crystallization phenomenon occurring at temperatures much lower than the bulk crystallization temperature (T_c) in polymers including PET, PEN and PVOH has previously been observed. However, whether or not this surface-specific crystallization is a phenomenon observable in all crystallizable polymers is still a question. Similarly, due to this greater mobility, phase separation may also be able to take place in the near-surface region of a polymer blend at a temperature much lower than the bulk phase separation temperature. Yet, no such investigation on polymer blends has been carried out. In addition, it is interesting to study the thin-film behaviours of a block copolymer that undergoes both phase separation and crystallization and compare these with corresponding bulk behaviour. In this thesis, the thin-film crystallization behaviour of polyamide 12 (PA12) in spin-cast films is presented together with some investigation of crystallization of polyamide 6 (PA6) and polystyrene. Polystyrene and poly(methyl methacrylate) (PS/PMMA) systems are used to illustrate the phase behaviours specific to the near-surface region. Finally, the microstructural evolution in high hard block content thermoplastic polyurethane (TPU) thin films on annealing has also been investigated. These TPUs have hard segments (HS) extended by 2 methyl 1,3 propanediol (2M13PD) or 1,5 pentanediol (15PD). With its flexible chains, PA12 crystallizes during spin coating forming as-spin-cast crystals with morphology that varies with solvent evaporation rate and film thickness. Despite the as spin-cast crystals, the free surface allows secondary surface crystallization of PA12 at an annealing temperature (T_a) roughly 20°C below the bulk T_c. The secondary surface crystals were indicated to exist in the most stable crystalline phase of PA12. Similar secondary surface crystallization has also been observed in the PA6 films but at a higher T_a due to the higher T_g of PA6. In addition, surface-specific crystals have been observed in PS (semicrystalline, likely due to some stereoregularity of composition), a polymer with bulky side groups. The PS surface crystals are, however, flat-on oriented showing the important effect of side groups on the morphology or growth shape of surface crystals. The discovery of these surface crystals supports the universality of surface specific crystallization. Using fast solvent quenching, it is possible to "freeze in" a structure containing both PS and PMMA in the near surface region. On annealing, surface-specific phase behaviours (observable as pits, undulations and aggregations) confined to the near-surface region take place first at temperatures around or just below the bulk polymer T_g, while bulk vertical phase separation and dewetting of PS to PMMA, forming holes, network structures and islands, occur at temperatures well above T_g. This surface specific phenomenon, being a result of the free surface, should be applicable to other phase separation systems with a free surface as well. An increase in the crystallinity of PS was found to promote the phase separation process, but the free surface effect is independent of the interplay between the crystallization and phase separation. Rather than having a two-phase morphology, as was previously observed in melt-quenched bulk samples, 2M13PD extended TPU spin-cast films showed a single-phase morphology as-spin-cast. However, the HS ordering, the formation of mesophase, the melting of HS ordered regions, and microphase mixing observed in thin films are consistent with the bulk results but with slightly different transition temperatures due to spatial confinement. With a more flexible chain extender, e.g. 15PD, the hard and soft phase separation is more limited. The thin film investigations have allowed a better understanding of the microstructural evolution in these high hard block content TPUs on annealing by imaging the morphology directly. A thin-film specific phenomenon: formation of large multilayer flat-on crystals, was also observed in these TPU thin films. These crystals are initially developed from preformed aggregations and are believed to be induced by the significant substrate effect in thin films and the free surface effect.

The development and use of nanotechnology towards theranostics (all-in-one disease diagnostics and therapeutic delivery) have been increasing in popularity in recent years, in particular the use of high capacity of nanomaterials to transport both imaging and therapeutic agents into pathological tissues or abnormal cells. In this work, biocompatible mesoporous silica nanoparticles (MSNs) that can be reliably endocytosed by cells are employed in the investigation of novel cancer treatment and magnetic resonance imaging (MRI). One of the principal aims is to develop T₁ contrast nanoparticles not only with extraordinarily high MRI contrast characteristics, but also tunability through surface chemistry and functional protein conjugation. In coupling paramagnetic Gd³⁺-centres to MSNs, one can effectively marry the advantages afforded by increased molecular bulk with those engendered by confined water environment inside the porous network. Specifically, through exclusively biasing paramagnetic Gd³⁺-centres in the internal spaces of nanoparticles, their mobility and interaction with water protons can be altered, significantly, with beneficial changes in molecular tumbling (τ_R), proton exchange (τ_M) and water diffusion (τ_D) within relaxation dynamics. These MRI nanoparticles with internalised Gd³⁺-centres are additionally used in the development of tunable/responsive contrast agents through vectoring protein conjugation. The relaxivity of MSNs can be tailored depending on the separation distances between proteins and nanoparticles; significantly, the simultaneous retention of both high MRI contrast and protein vectoring is achieved by the insertion of long polyethylene glycol (PEG) chain. The image contrast can also be reversibly gated through the competitive displacement of surface proteins by their partner proteins. Specifically, these responsive nanoparticles possess a low contrast resulting from restricted water accessibility when protein moieties are conjugated on the particles, whereas the removal of proteins causes a transition of contrast from a low to high state. The MSNs synthesised in this work are used not only in diagnostic imaging but also in the delivery of therapeutic agents for cancer therapy. The agents can be either physically encapsulated inside the pores or chemically conjugated on the nanoparticles. For the former, their loading and release efficiencies are tunable by the electrostatic interactions with particle surface functional groups; while in the latter case, their retention on nanoparticles, as opposed to being released, plays an important role in the effectiveness of cancer treatment that is achieved by trigging programmed cell death (apoptosis) in this work. This nanoparticle conjugation secures the proteins’ activity by facilitating their bypass of proteolytic degradation. Significantly, specially designed nanoparticles that demonstrate endo/lysosomal escape capability can reliably deliver therapeutic cytochrome c to cell cytosols for the initiation of a caspase cascade within apoptosis with high efficacy.

This project addressed two main problems pertaining to Al₂O₃-FeAl2O4 nanocomposites developed via solid state precipitation: the mechanisms for precipitation in ceramic solid solution via reduction reaction, and the mechanisms for the improved mechanical properties and wear resistance of the developed Al2O3-FeAl2O4 nanocomposites. A model was proposed for precipitation in ceramic solid solutions via reduction reactions (the PRCS model). The thermodynamics of reduction reactions during aging treatments under various atmospheres were calculated and discussed relative to the second phase precipitate formation. Attempts were made to measure the corresponding diffusion kinetics using a new theory developed here based on volume fraction profiles of second phase particles in the aged samples. It was found that the measured apparent oxygen vacancy diffusivities conform well to the oxygen vacancy grain boundary diffusion coefficients reported in the literature, and the measured apparent matrix diffusivity conforms well to the Fe3+ ion matrix diffusion coefficients reported in literature. Based on the thermodynamics calculations, diffusion kinetics and some essential mechanisms that were discussed, the PRCS model was proposed. This has two aspects: macroscopic and microscopic. The macroscopic aspect of PRCS model was mainly used to explain the general aspects of microstructure and the distribution of intergranualar second phase particles. The microscopic aspect of the PRCS model was mainly used to explain the precipitation of intragranualar nanoparticles. The mechanical properties, thermal residual stress and wear resistance of selected Al2O3-FeAl2O4 nanocomposites were measured. The results revealed that the Al2O3-FeAl2O4 possessed improved fracture toughness (by around 46%), flexural strength (by around 30%) and abrasive wear resistance (by a factor of around 5) with respect to monolithic alumina. Several mechanisms were proposed to explain the improvements in both mechanical properties and wear resistance. Compressive residual stress was found in the surface layer of Al2O3-FeAl2O4 nanocomposites due to the thermal expansion coefficient mismatch between surface layer and bulk parts. Such residual stress was also interpreted as the main reason for the improvements in both mechanical properties and wear resistance.

This thesis presents applications of high resolution secondary ion mass spectrometry (NanoSIMS) analysis for stable isotope imaging in biological samples. These projects were designed to explore the potential applications of NanoSIMS analysis, and to develop protocols and novel methodologies to visualize and quantify biological processes. Working with collaborators in the UK and USA, I have applied NanoSIMS analysis to study 3 research areas, including molecule interactions, single cell metabolisms and lipid imaging in tissues. Antimicrobial peptides (AMPs) play important role in the immune system, and understanding how AMPs interact with cell membranes can provide useful information to design new therapies to control infection. The pore structures and dynamics of the interaction of AMPs with membranes has been visualized for the first time and confirmed with combined AFM and NanoSIMS analysis. A correlative backscattered electron (BSE) imaging and NanoSIMS analysis methodology has been developed to study glutamine metabolism in single cancer cells. This method enables us to measure the chemical information in specific organelles in these cells and can be widely applied to study metabolisms and to trace the uptake of labelled molecules in biological matrices. Quantitative analysis on the effects of hypoxic conditions and the PYGL gene were studied. Applying correlative BSE and NanoSIMS analysis, I also studied lipid uptake mechanisms in various mouse tissues, including brown adipose tissue, heart, intestines, liver and skeletal muscle, mainly focused on a recently discovered protein, GPIHBP1, and its function in the lipid uptake process. TRL margination was proved to depend on the GPIBP1-LPL complex, and 3 stages of lipid transport from capillary lumen to lipid droplets was also visualized by combined BSE and NanoSIMS analysis.

The successful utilization of carbon nanomaterials in future electron spin-based technologies is highly dependent upon the ability to control their assembly at the nanoscale to form tailored solid-state architectures. Spin active metallofullerenes (MFs), Sc@C₈₂ and La@C<sub>82,/sub>, can be self assembled in 3D fullerene crystals or inside a carbon nanotube to form peapod structures. Single walled carbon nanotubes (SWCNTs) are an architect material to potentially allow the formation of 1-D spin chains. SWCNTs should be optimised to allow formation of spin chains and free of magnetic catalyst and carbon impurities, which have previously limited investigations of SWCNT spin properties. To address this, SWCNTs produced by laser ablation with a non-magnetic PtRhRe catalyst were purified through a multiple step centrifugation process in order to remove amorphous carbon and catalyst impurities. Centrifugation of SWCNT solutions resulted in sedimentation of carbon nanotube bundles containing clusters of catalyst particles, while isolated nanotubes with reduced catalyst particle content remained in the supernatant. Electron paramagnetic resonance (EPR) signals were detected only for samples which contained catalyst particles, with the ultracentrifuged SWCNTs showing no EPR signal at X-band (9.4 GHz) and fields ≤0.4 T. Integration of MFs into future devices requires a clear understanding of the nature of the spin and spin-spin interactions. Evaluating the spin properties of MFs, in both 3D (crystals) and 1D (peapods), will identify the spin-spin interactions and the affect of the surrounding SWCNT. Diluting spin active Sc@C₈₂ and La@C₈₂ MFs in a diamagnetic C₆₀ matrix, between 0.4% and 100%, permitted the tuning of the mean fullerene separation and thus interfullerene spin interactions. In dilute concentrations of MFs the hyper ne structure was resolved in EPR and with increasing concentration exchange narrowing was observed as a single narrow EPR peak. Encapsulation of Sc@C₈₂ MFs, of varying dilutions, into purified SWCNTs allowed formation of highly ordered 1-D array of metallofullerenes. Changing the spin environment from 3D crystal to 1D peapod resulted in the loss of the observed hyperfine structure in EPR. A single narrow peak was observed for Sc@C₈₂:C₆₀ peapods, indicating significant affect of the surrounding SWCNT structure upon the spin interactions of 1D metallofullerenes. Peapods of Ce@C₈₂ showed a similar EPR signal, suggesting that the observed narrow peak arises from charge transfer between the MF cage and the surrounding SWCNT.

Poly(vinyl alcohol) (PVA) is a polymer used in numerous applications, principally those in which its high water solubility is a desirable asset. However there are also areas where PVA is limited by its inherent solubility (for example some specific environments in the biomedical field). This work has sought to overcome such limits by manipulating the surface of PVA in order to propose various means by which the surface solvent resistance might be increased while maintaining the bulk properties of the polymer. Both chemical and physical modifications have been tried and in each case progress has been made towards insolubilizing a single surface of the polymer when in film form. Grafting various species onto the surface of PVA was successfully performed. It is believed that such species bonded to the PVA via attachment to the hydroxyl groups (though this has not been proven conclusively). The data contained herein has led to the conclusion that the primary factor in reducing solubility this way is the removal of the hydroxyl groups, and not the attachment of specifically highly hydrophobic molecules. Introducing permanent cross-links into the surface region has been attempted via various routes. The data recorded shows promise however the system is far from optimised. The biggest challenge remaining is to optimise the depth of material cross-linked. Some steps have been made towards understanding and controlling this parameter though there is much scope for further investigation. The methods used have built on those used for bulk cross-linking and as such are new for the case of surface specific treatment. An interesting phenomenon in some semi-crystalline polymers reported in recent years is that of surface specific crystallization. This effect has been successfully induced and observed in PVA to produce what is believed to be a highly crystalline surface layer, and crystalline regions of PVA are generally accepted to be more water resistant than amorphous ones. In summary, in this work several surface-specific treatments for PVA have been trialled, providing options for post-film forming modification to reduce the surface water sensitivity whilst retaining the bulk properties of the polymer.

The behaviour of nitrogen in silicon is investigated using the dislocation unlocking technique. Specimens containing well-ordered arrays of dislocations are isothermally annealed for a controlled duration, during which nitrogen segregates to and pins the dislocations. The stress required to unlock the dislocations is then measured by three-point bending at elevated temperature. By analysing the dependence of this unlocking stress on anneal duration and temperature, information about nitrogen's transport and interaction with dislocations can be deduced. Experiments are performed at anneal temperatures of 500 - 1050C using float-zone silicon with [N] = 2x10^15 cm^-3. The results are analysed to give an expression for nitrogen's effective diffusivity of D = 173,000 exp(-3.24eV/kT)cm^2 s^-1 in the 500 - 750C range, showing for the first time that nitrogen transport at low temperatures behaves in the same way as measured at higher temperatures by other groups using secondary ion mass spectrometry. If analysed in terms of monomer-dimer dissociative transport, the results give a nitrogen monomer diffusivity of D_1 = 28 exp(-(1.1 to 1.4 eV)/kT) cm^2 s^-1, which is similar to that found by another analysis in the literature. The measurements also show that nitrogen's dislocation locking strength measured at 550C is dependent on anneal temperature, peaking at 600 - 700C and falling towards zero above 1000C. The dislocation unlocking technique itself is also investigated and characterized. It is found that the measured unlocking stress is dependent on the three-point bend duration, falling with increasing duration. Analysis of these results in terms of the theory of release of dislocations from pinning points indicates that nitrogen dislocation locking is likely to be by an atomic species. This effect also has implications for the results of previous nitrogen dislocation unlocking experiments, and the technique has been modified so that a standardised set of conditions is used for every test. Other measurements show that nitrogen's dislocation locking effect is lessened by the presence of transition metal contamination, and that dislocation velocity in silicon may be affected by the nitrogen present in the material. A modified dislocation unlocking technique is developed to measure dislocation locking from near-surface ion-implanted impurities. Results from heavily N-implanted silicon show that nitrogen implantation can provide additional dislocation locking strength to that already given by the oxygen in the material. The scale of the dislocation locking effect in these experiments may provide evidence that nitrogen's effective diffusivity is reduced at high concentrations, indicating that nitrogen transport may be by a dissociative mechanism.

Tungsten will be a key material for the plasma-facing components in future fusion devices. Its mechanical performance under neutron irradiation will strongly influence the lifetime of these devices. Pure tungsten has been subjected to a variety of irradiating species - tungsten ions, helium ions and fission neutrons - between 500&deg;C and 900&deg;C and the change in mechanical properties measured by micro-mechanical testing methods. Pure tungsten has been ion-irradiated using self-ions and helium ions at 500&deg;C and 800&deg;C. Nanoindentation has been performed on all specimens, and the 800&deg;C specimens have been tested at temperatures up to 750&deg;C using high-temperature nanoindentation. The irradiation temperature has no effect on the hardening of tungsten. Hardening from self-ion irradiation has not saturated by 4.5 dpa with an increase in hardness of 3.3 GPa. The hardening from helium implantation is only 0.73 GPa, and a comparison with literature shows that this hardening only depends on the concentration of the injected helium. The difference is likely due to the much smaller defect size of helium-vacancy clusters when compared to dislocation loops. High-temperature nanoindentation shows that helium-implanted tungsten softens rapidly, with the hardening from the radiation damage becoming negligible above 450&deg;C. Self-ion implanted tungsten does not soften by 650&deg;C, again likely due to the size difference of the defects. Micro-mechanical tests - namely micro-cantilever bending - have been used to investigate the plastic and fracture characteristics of tungsten before and after irradiation. Plastic behaviour is dominated by size effects due to the 3 &mu;m depth of the implanted layers, which makes nanoindentation a better method for investigating radiation damaged layers. In fracture testing, fracture is rarely seen. Using the yield stress to calculate fracture toughness, the hardening from irradiation damage results in an increase in fracture toughness from 2.2 MPa&radic;m to 6.0 MPa&radic;m. The work of deformation at 1&percnt; is also increased after irradiation from 7.2 x 10^-11 Nm to 2.8 x 10^-10 Nm, implying that the implanted damage is not leading to an increase in embrittlement by reducing K^1c. Neutron irradiated tungsten also shows an increase in fracture toughness after irradiation from 6.5 MPa&radic;m to 14.5 MPa&radic;m. However, the BDTT increases by &Tilde; 100&deg;C in poly-crystal tungsten and &Tilde; 500&deg;C in single-crystal tungsten. The difference in BDTT does not exist in the unimplanted material. The change after irradiation is likely due to the fine (&tilde; 3 &mu;m) grain size and 900&deg;C irradiation temperature causing a significant amount of the displacement damage to be absorbed at the grain boundaries. The hardness of neutron irradiated and ion irradiated tungsten is very close: 10.4 GPa and 11.2 GPa respectively, demonstrating the ions are likely well-representing the neutron damage in pure tungsten.

The synthetic biodegradable polymer poly(lactide-co-glycolide) (PLGA) has been widely explored as substrate biomaterials for controlled drug delivery and tissue engineering. ECM component heparin and bone mineral hydroxyapatite (HA) are attractive biomaterials which can functionalize the PLGA surface to improve cell cell response and to bring in the dual growth factor delivery, because heparin and HA both can improve cell responses and bind with various proteins. To combine the osteoconductivity of HA and the controlled drug release of PLGA microspheres, HA coated PLGA microspheres were developed by a 3 hour rapid HA precipitation on the PLGA microsphere surface. Effects of various fabrication parameters on microsphere and HA coating morphology were evaluated. This core-shell composite worked as a dual drug delivery device and demonstrated better cell cell response than PLGA microspheres without HA coating. Three different methods, including osmogen, extractable porogen and gas-foaming porogen, were evaluated to fabricate porous microspheres as injectable cell scaffolds in the tissue engineering. The gas-foaming method produced covered porous PLGA microspheres, on which a skin layer covered all the surface pores. The skin layer was hydrolysed by NaOH to control the surface porosity. The modified open porous microspheres have large continued surface areas between pores, which provided more continued areas for cell adhesion. The porous microspheres with controllable surface porosity and large surface continuity between pores could be novel injectable cell scaffolds. Heparin was immobilized on the open porous PLGA microspheres by a facile layer-by-layer assemble to combine the advantages of porous structure and the protein binding from heparin. The heparin-coated porous microspheres promoted cell adhesion, spreading, proliferation and osteogenic differentiation. Growth factor-like protein lactoferrin was immobilized on the heparin coated porous microspheres, which further enhanced MG-63 proliferation and osteogenic differentiation. The heparin-coated porous microspheres are promising multi-functional devices for controlled drug delivery and injectable cell delivery.