Experiments and analysis in this thesis advance the understanding of critical issues in the carrier transport properties of InAs and InAs/GaAs core/shell heterostructure nanowires (diameter 30-60 nm) grown by molecular beam epitaxy. Effects of robust sub-band quantization structure on the gate-voltage dependence of conductance are observed up to 77 K in a single InAs nanowire with diameter 34\pm2 nm. Electronic field effect mobility at 300 K and 30 K are typically 2000-4000 cm^2V^-1s^-1 and 10000-20000 cm^2V^-1s^-1. Strain induced by lattice mismatch in epitaxial core/shell InAs/GaAs heterostructure nanowires is found to relax by formation of dislocations, correlated with nearly one order of magnitude suppression of room temperature field effect mobility compared with bare InAs nanowires. The carrier transport properties of Mn-doped ZnO nanowires were also investigated, where despite the large bandgap, conductivity is not thermally activated, and carrier mobility is consistent with strong degeneracy of the electron gas at 10 K. A novel method was developed providing the first experimental characterization of the quasi-equilibrium gate-voltage dependent surface potential in nanowire field-effect transistors, based on statistics of charging/discharging of a single Coulomb impurity evident in a random telegraph signal, which succeeds in nanostructures with tiny (attofarad) gate capacitance, where similar capacitance-voltage methods are challenging or impossible. We find that the evolution of channel potential with gate voltage is suppressed in the transistor's accumulation regime due to the screening effects of surface states with D_ss=1-2\times10^{12} cm^-2eV^-1. The gate voltage dependence of the random telegraph signals were used as a novel probe to spectroscopically study strong carrier reflection by single Coulomb impurities in nanowires. Reflection probabilities R=0.98-0.999 approach unity for an electron gas with density n=30-10 /micron in 30 nm diameter, 1 micron long InAs nanowires at 30 K. Results were compared with microscopic theory of electron scattering by Coulomb impurities in nanowires with dielectric confinement, i.e low dielectric constant surroundings. The latter, which is known to enhance the bare Coulomb interaction and excitonic binding energy, is an essential ingredient for the strong scattering in this regime, and in small diameter nanowires causes a breakdown in linear screening. Extending this, we show that InAs nanowires can operate is extremely sensitive charge sensors with sensitivity 60 micro eHz^-1/2 at high temperatures (200 K), a combination of characteristics that is not achieved by existing technology. Strong electrostatic coupling of a single charge to the conducting electron gas in the nanowire is enabled by miniaturization of nanowire diameter, operation in a regime of carrier density where the electronic screening length exceeds the nanowire diameter, and dielectric confinement. Finally, single ZnSe nanowire photodetectors are fabricated and studied. Peak responsivity at 2.0 V bias is 20 A/W at room temperature, similar to that of the best epitaxial ZnSe photodetectors. The high responsivity is due to a photoconductive gain g=500, the ratio of carrier lifetime to carrier transit time. The former is enhanced at room temperature due to rapid selective trapping of one species of excited carriers by surface states.

Ionic liquids are molten salts with melting points below 100 °C and they consist entirely of cations and anions. The development of ionic liquids, especially air and water stable types, has attracted extensive attention since they have outstanding physical properties. Part I of the study focused on the pre-electrolysis process performed to remove impurities from the ionic liquid, 1-butyl-1-methyl-pyrrolidinium bis(tri-fluoromethylsulfonyl)imide, ([BMP]Tf2N). Part II investigated the electroreduction of TaF5 and NbF5 from room temperature ionic liquid at 100 °C at a wide range of potentials and different time durations for the purpose of determining the optimal conditions for the electrodeposition of tantalum. The study was carried out using potentiostatic polarization for the pre-electrolysis treatments and electrodeposition and cyclic voltammetry to study the behaviour of the liquid at various stages. Potentiostatic depositions were complemented by scanning electron microscopy (SEM)/energy-dispersive x-ray analysis (EDX), x-ray photoelectron spectroscopy (XPS) and x-ray diffraction (XRD) for characterization of the electrodeposits.

Compliant nanoporous gold is investigated with regards to its elastic modulus and deformation mechanisms. Samples are fabricated by dealloying AgAu alloys at elevated temperature and reduced dealloying potential compared with conventional methods in the literature. This procedure minimizes cracking and shrinkage that is typical from other dealloying methods. Furthermore, samples are found to be more compliant while immersed in water. Samples were tested in cyclic compression using a piezoelectric compression rig. Testing showed that the wet samples become stiffer upon drying and the effect is reversible with short drying times. This is attributed to microstructural effects as the ligament network becomes more connected as a result of drying, effectively shifting the dominant deformation mode from three-point bending to cantilever bending. At longer dry times, the effect is irreversible due to contact weld formation. Preliminary results on sputter deposited AgAuPt alloys show altered dealloying kinetics and crack formation.

Recent advances in the field of bionanotechnology have enabled researchers to design a variety of tools to detect, image and monitor biological process in cells. Despite this progress, the limited understanding of nanomaterial-cellular interactions has hindered the widespread use of these nanomaterials in biological systems. In this thesis, we examined the potential effects of metallic nanoparticle geometry on important cellular processes such as membrane trafficking, intracellular transport and subcellular signalling. We found that the size of nanoparticles plays an important role on their ability to interact with the cell surface receptors thus dictating their subsequent ability to activate intracellular signalling cascades. Interestingly, trafficking of these nanoparticles was dependent on their size due to biochemical and thermodynamical constraints. These findings suggest that nanomaterials actively interact with biological systems, thus, directly modulating vital cellular processes. In addition, by utilizing various physical and chemical properties of nanomaterials, we developed a novel class of hybrid nanoscaled carrier systems capable of delivering semiconductor quantum dots (QDs) into live cells without inducing membrane damage. Using biodegradable polymeric nanoparticles, bioconjugated QDs were encapsulated and delivered into trafficking vesicles of live cells. The environmentally sensitive surface charge of the polymeric nanoparticles exhibited positive zeta potential inside acidic endo-lysosomes, thus enabling their escape from the vesicular sequestration into the cytosol. Hydrolytic-induced degradation then releases the bioconjugate QDs for active labelling of subcellular structures for real-time studies. Unlike previously described intracellular QD delivery methods, the proposed system offers an efficient way to non-invasively deliver bioconjugated QDs without inducing cell damage, enabling researchers to accurately monitor cellular processes in real-time. The understanding of both physical and chemical properties of nanomaterials is crucial to the design of biocompatible nanosystems to study fundamental processes in biological systems. Here, we demonstrated that both the size and surface chemistry of nanoparticles can be modified to obtain desired biological responses. Future experimental efforts to study other physical and chemical properties could allow the development of more sophisticated and effective platforms for biological applications.

Ionic liquids are molten salts with melting points below 100 °C and they consist entirely of cations and anions. The development of ionic liquids, especially air and water stable types, has attracted extensive attention since they have outstanding physical properties. Part I of the study focused on the pre-electrolysis process performed to remove impurities from the ionic liquid, 1-butyl-1-methyl-pyrrolidinium bis(tri-fluoromethylsulfonyl)imide, ([BMP]Tf2N). Part II investigated the electroreduction of TaF5 and NbF5 from room temperature ionic liquid at 100 °C at a wide range of potentials and different time durations for the purpose of determining the optimal conditions for the electrodeposition of tantalum. The study was carried out using potentiostatic polarization for the pre-electrolysis treatments and electrodeposition and cyclic voltammetry to study the behaviour of the liquid at various stages. Potentiostatic depositions were complemented by scanning electron microscopy (SEM)/energy-dispersive x-ray analysis (EDX), x-ray photoelectron spectroscopy (XPS) and x-ray diffraction (XRD) for characterization of the electrodeposits.

Compliant nanoporous gold is investigated with regards to its elastic modulus and deformation mechanisms. Samples are fabricated by dealloying AgAu alloys at elevated temperature and reduced dealloying potential compared with conventional methods in the literature. This procedure minimizes cracking and shrinkage that is typical from other dealloying methods. Furthermore, samples are found to be more compliant while immersed in water. Samples were tested in cyclic compression using a piezoelectric compression rig. Testing showed that the wet samples become stiffer upon drying and the effect is reversible with short drying times. This is attributed to microstructural effects as the ligament network becomes more connected as a result of drying, effectively shifting the dominant deformation mode from three-point bending to cantilever bending. At longer dry times, the effect is irreversible due to contact weld formation. Preliminary results on sputter deposited AgAuPt alloys show altered dealloying kinetics and crack formation.

Experiments and analysis in this thesis advance the understanding of critical issues in the carrier transport properties of InAs and InAs/GaAs core/shell heterostructure nanowires (diameter 30-60 nm) grown by molecular beam epitaxy. Effects of robust sub-band quantization structure on the gate-voltage dependence of conductance are observed up to 77 K in a single InAs nanowire with diameter 34\pm2 nm. Electronic field effect mobility at 300 K and 30 K are typically 2000-4000 cm^2V^-1s^-1 and 10000-20000 cm^2V^-1s^-1. Strain induced by lattice mismatch in epitaxial core/shell InAs/GaAs heterostructure nanowires is found to relax by formation of dislocations, correlated with nearly one order of magnitude suppression of room temperature field effect mobility compared with bare InAs nanowires. The carrier transport properties of Mn-doped ZnO nanowires were also investigated, where despite the large bandgap, conductivity is not thermally activated, and carrier mobility is consistent with strong degeneracy of the electron gas at 10 K. A novel method was developed providing the first experimental characterization of the quasi-equilibrium gate-voltage dependent surface potential in nanowire field-effect transistors, based on statistics of charging/discharging of a single Coulomb impurity evident in a random telegraph signal, which succeeds in nanostructures with tiny (attofarad) gate capacitance, where similar capacitance-voltage methods are challenging or impossible. We find that the evolution of channel potential with gate voltage is suppressed in the transistor's accumulation regime due to the screening effects of surface states with D_ss=1-2\times10^{12} cm^-2eV^-1. The gate voltage dependence of the random telegraph signals were used as a novel probe to spectroscopically study strong carrier reflection by single Coulomb impurities in nanowires. Reflection probabilities R=0.98-0.999 approach unity for an electron gas with density n=30-10 /micron in 30 nm diameter, 1 micron long InAs nanowires at 30 K. Results were compared with microscopic theory of electron scattering by Coulomb impurities in nanowires with dielectric confinement, i.e low dielectric constant surroundings. The latter, which is known to enhance the bare Coulomb interaction and excitonic binding energy, is an essential ingredient for the strong scattering in this regime, and in small diameter nanowires causes a breakdown in linear screening. Extending this, we show that InAs nanowires can operate is extremely sensitive charge sensors with sensitivity 60 micro eHz^-1/2 at high temperatures (200 K), a combination of characteristics that is not achieved by existing technology. Strong electrostatic coupling of a single charge to the conducting electron gas in the nanowire is enabled by miniaturization of nanowire diameter, operation in a regime of carrier density where the electronic screening length exceeds the nanowire diameter, and dielectric confinement. Finally, single ZnSe nanowire photodetectors are fabricated and studied. Peak responsivity at 2.0 V bias is 20 A/W at room temperature, similar to that of the best epitaxial ZnSe photodetectors. The high responsivity is due to a photoconductive gain g=500, the ratio of carrier lifetime to carrier transit time. The former is enhanced at room temperature due to rapid selective trapping of one species of excited carriers by surface states.

Half of the sun’s power lies in the infrared. As a result, the optimal bandgaps for solar cells in both the single-junction and even the tandem architectures lie beyond 850 nm. However, progress in low-cost, large-area, physically-flexible solar cells has instead been made in organic and polymer materials possessing absorption onsets in the visible. Recent advances have been achieved in solution-cast infrared photovoltaics through the use of colloidal quantum dots. Here we report stable solution-processed photovoltaic devices having 3.6% power conversion efficiency in the infrared. The use of a strongly-bound bidentate linker, benzenedithiol, ensures device stability over weeks. We investigate in detail the physical mechanisms underlying the operation of this class of device. We find that diffusion of electrons and holes over hundreds of nanometers through our PbSe colloidal quantum dot solid is chiefly responsible for the high external quantum efficiencies obtained in this new class of devices.

Semiconductor nanowires (NWs) are anticipated to play a crucial role in future electronic and optoelectronic devices. Their practical applications remain hindered by an urging need for feasible strategies to tailor their optical and electronic properties. Strategies based on strain and alloying are limited by issues such as defects, interface broadening and alloy scattering. In this thesis, a novel method to engineer the optoelectronic properties based on strain-free periodic structural modulations in chemically homogeneous Nanowire Twinning Superlattices (NTSLs) is experimentally demonstrated. NTSLs are an emerging new class of nanoscale material, composed of periodically arranged rotation twin-planes along the length of NWs. The main objective of this thesis is to establish the relationship between the electronic energy band gap (Eg) and the twin-plane spacing (d) in NTSLs, quantified using a periodicity parameter, based on ZnSe. ZnSe was chosen because of its excellent luminescence properties, and potential in fabrication of optoelectronic devices in the near-UV and blue region of the spectrum. A prerequisite to establishing this correspondence is a prior knowledge of the photoluminescence (PL) response and the nature of fundamental optical transitions in defect-free single crystal ZnSe NWs with zinc-blende (ZB) and wurtzite (WZ) crystal structures. There has been no systematic work done yet on understanding these fundamental optical processes, particularly on single NWs and in relation to their crystalline microstructure. Therefore, the secondary objective of this thesis is to study the influence of native point defects on the optical response of single ZnSe NWs in direct relation to their crystalline microstructure. The PL response from single ZB and WZ NWs was determined unambiguously, and excitonic emission linewidths close to 1 meV were observed, which are the narrowest reported linewidths thus far on ZnSe NWs. Based on this and extensive optical and structural characterization on individual NTSLs, a linear variation in Eg is shown through a monotonic shift in PL peak position from ZnSe NTSLs as a function of d, with Eg's that lie between those of ZB and WZ crystal structures. This linear variation in Eg was also validated by ab Initio electronic structure calculations. This establishes NTSLs as new nanoscale polytypes advantageous for applications requiring tunable band gaps.

In vitro grown cartilage is functionally inferior to native tissue, and improvements in its quality should be attempted so it can be used therapeutically. In these studies we investigated the effects of cell shape on tissue quality through alteration of substrate geometry and application of mechanical stimuli. Articular chondrocytes were isolated and cultured on the surface Ti-6Al-4V substrates with various geometries. When cultured on fully porous titanium alloy substrates, chondrocyte spreading was enhanced over those grown on substrates with solid bases. Chondrocytes which remained round did not synthesize significant amounts of matrix and were thus unable to form cartilaginous tissue. In contrast, chondrocytes which were directed to spread to a limited amount, resulting in a polygonal morphology, accumulated significantly more matrix molecules and in time formed cartilage-like tissue. Computational fluid dynamics analyses demonstrated that cells on fully porous substrates experience time-dependent shear stresses that differ from those experienced by cells on substrates with solid bases where media flow-through is restricted. Integrin-blocking experiments revealed that integrins are important regulators of cell shape, and appeared to influence the accumulation of collagen and proteoglycans by chondrocytes. Furthermore, compressive mechanical stimulation induced a rapid, transient increase in chondrocyte spreading by 10 minutes, followed by a retraction to pre-stimulated size within 6 hours. This has been shown to be associated with increased accumulation of newly synthesized proteoglycans. Blocking the α5β1 integrin, or its β1 subunit, inhibited cell spreading and resulted in a partial inhibition of compression-induced increases in matrix accumulation, thereby substantiating the role of β1 integrins in this process. These results suggest that both fluid induced shear forces and compressive forces regulate chondrocyte matrix accumulation by altering cell morphology, which is mediated by integrins. Identifying the molecular mechanisms that influence chondrocyte shape and thus tissue formation may ultimately lead to the development of a tissue that more closely resembles native articular cartilage.