No / Nanotechnologies for intracellular delivery are of great value in clinical and biological research. Diamond nanoneedle arrays are a novel and attractive platform to facilitate drug delivery with minimal cytotoxicity. Using our technique, the cellular membranes can be temporarily disrupted for enhanced diffusion of drug molecules to cytoplasm. Herein we show that this technique is applicable to deliver different types of anticancer drugs into a variety of cell lines, although the membrane of each cell line possesses varied rigidity and hardness and each drug has its own unique properties and targets. When anticancer drugs and nanoneedle arrays are collaboratively used to treat cancer cells, the cell viability dramatically decreases by up to 40 % in comparison with the cells treated with drugs only. Attractively, therapeutic molecules can be efficiently delivered to drug-resistant cells with the aid of nanoneedle arrays. The combination of diamond nanoneedle arrays and anticancer drug cisplatin can decrease the viability of A549 cisplatin-resistant cells to about 60 %, while the cells only treated with the same concentration of drug are essentially not affected due to their drug resistance. These results indicate that dense nanoneedle arrays represent an effective approach to enhance the delivery of biological molecules to different types of cells. Such approach will certainly be beneficial to microbiological research and clinical applications in the future.

This thesis is an attempt to understand ways to improve thermo-mechanical and structural properties of nano-structured materials. A detailed study on computational design and analysis of metallic nanowires is carried out. Molecular dynamic simulation method is applied. In particular, FCC metallic nanowires, NiAl, and CuZr nanowires are studied. Various bottom-up approaches are suggested with improved structural and thermo¬mechanical properties. In the first part of the thesis, Cu nanowires are considered. Existence of a novel and stable pentagonal multi-shell nanobridge structure of Cu under high strain rate tensile loading is reported. Such a structure shows enhanced mechanical properties. A three-fold pseudo-elastic-plastic shape recovery mechanism in such nanowires is established. This study also shows that the length of the pentagonal nanobridge structures can be characterized by its inelastic strain. It is also reported that an initial FCC structure is transformed into a new HCP structure. The evidence of HCP structure is confirmed with the help of experimental data published in the literature. Subsequent to the above study, a novel mechanism involving coupled temperature-stress dependent reorientation in FCC nanowires is investigated. A detailed map is generated for size dependent stress-temperature induced solid-solid reorientation in Cu nanowires. In the second part of the thesis, deformation mechanisms in NiAl based intermetallic nanowires are studied. A novel mechanism of temperature and cross-section dependent pseudo-elastic/pseudo-plastic shape and strain recovery by an initial B2 phase of NiAl nanowire is reported. Such a recoverable strain, which is as high as ~ 30%, can potentially be utilized to realize various types of shape memory and strain sensing phenomena in nano-scale devices. An asymmetry in tensile and compressive yield strength behavior is also observed, which is due to the softening and hardening of the nanowires under tensile and compressive loadings, respectively. Two different deformation mechanisms dominated by twinning under tension and slip under compression are found. Most interestingly, a superplastic behavior with a failure strain of up to 700% in the intermetallic NiAl nanowires is found to exist at a temperature of 0.36Tm. Such superplastic behavior is attributed to the transformation of the nanowire from a crystalline phase to an amorphous phase after yielding of the nanowire. In the last part the work, another type of nanowires having Cu-Zr system is considered. A novel stress induced martensitic phase transformation from an initial B2 phase to BCT phase in a CuZr nanowire under tensile loading is reported. It is further shown that such a stress induced martenistic phase transformation can be achieved under both tensile as well as compressive loadings. Tensile-compressive asymmetry in the stress-strain behavior is observed due to two different phase transformation mechanisms having maximum transformation strains of ~ 5% under compressive loading and ~ 20% under tensile loading. A size and temperature dependent tensile phase transformation in the nanowire is also observed. Small nanowires show a single step tensile phase transformation whereas the nanowires with larger size show a two step deformation mechanism via an intermediate R-phase hardening followed by R-phase yielding. A study of energetic behavior of these nanowires reveals uniform distribution of stress over the nanowire cross-section and such stress distribution can lead to a significant improvement in its thermo-mechanical properties. Similar improvement is demonstrated by designing the nanowires via manipulating the surface configuration of B2-CuZr system. It is found that the CuZr nanowires with Zr atoms at the surface sites are energetically more stable and also give a uniform distribution of stresses across the cross-section. This leads to the improvement in yield strength as well as failure strain. An approach to design energetically stable nano-structured materials via manipulating the surface configurations with improved thermo-mechanical properties is demonstrated which can help in fundamental understanding and development of similar structures with more stability and enhanced structural properties. Further ab-initio and experimental studies on the confirmation of the stability of the nanowires via manipulating the surface site is an open area of research and related future scopes are highlighted in the closure.

The main focus of this thesis work has been the study of domain wall (DW) dynamics in disordered cylindrical nanomagnets. The study attempts to accurately quantify the stochasticity associated with driven (temperature/magnetic field/spin-torque) DW kinetics. Our results as summarized below, are particularly relevant with regard to the technological advancement of DW based magnetoelectronic devices. 1. Temperature dependent noise measurements showed an exponential increase in noise mag-nitude, which was explained in terms of thermally activated DW depinning within the Neel-Brown framework. The frequency-dependence of noise also indicated a crossover from nondiffusive kinetics to long-range diffusion of DWs at higher temperatures. We also observed strong collective depinning, which must be considered when implementing these nanowires in magnetoelectronic devices. 2. Our noise measurements were sensitive enough to detect not only the stochasticity in DW propagation (diffusive random walk) but also their nucleation in the presence of magnetic field down to a single DW unit inside an isolated single Ni nanowire. Controlled injection and detection of individual DWs is critical in designing DW based memory devices. 3. The spectral slope of noise was observed to be sensitive to DWkinetics that reveals a creep-like behavior of the DWs at the depinning threshold, and diffusive DW motion at higher spin torque drive. Different regimes of DW kinetics were characterized by universal kinetic exponents. Noise measurements also revealed that the critical current density and DW pinning energy can be significantly reduced in a magnetically coupled vertical ensemble of nanowires. This was attributed to strong dipolar interaction between the nanowires. Our results are particularly important in view of recent proposals for low power consumption magnetic storage devices that rely on DW motion. In all our experiments, the critical magnetic field/current density, required to set the DWs in duffusive kinetics, were found to be much smaller than the reported values for nanostrips. This could be attributed to the circular cross section of nanowires, where massless DWs results in the absence of Walker breakdown and hence in zero critical current density. At present the contribution from the non-adiabaticity, which acts as an effective field and can reduce the crit- ical current density, can not be denied. The main di±culty in quantifying the non-adiabatic spin-torque is that not only does it contain contributions due to non-adiabatic transport but also due to spin-relaxation provided by magnetic impurities or the sources for spin-orbit scattering. Fortunately, in cylindrical nanomagnet, non-adiabaticity does not affect the DW motion. There- fore, cylindrical NWs may be promising candidate for future magnetic storage devices. However, a systematic experimental study of DW dynamics in cylindrical nanomagnets is lacking. In chapter 7, silver nanowires (AgNWs) are shown to be stabilized in fcc or hcp crystal structure, depending on the electrochemical growth conditions. The AgNWs stabilized in hcp crystal structure are shown to exhibit exotic structural properties i.e. ultra low noise level, thermally driven unconventional structural phase transformation, and time dependent structural relaxation. Ultra noise level makes hcp AgNWs suitable for application in nanoelectronics and the structural transformation may be exploited for use in smart materials. Though time resolved transmission electron microscopy and noise measurements provide some understanding of the hcp AgNWs formation, the precise growth mechanism is still not clear. Future scope of the work The results in this thesis provide the groundwork for a good understanding of stochastic DW kinetics in isolated as well as ensemble of magnetic nanocylinders. Some extensions to this work that would help expand and strengthen the results, are listed below; 1. In all the nanocylinders used for our experiments the source of stochasticity in DWkinetics were randomly distributed structural defects. For a controlled injection and detection of DWs between the voltage probes, it would be of great importance to fabricate artificial notches (pinning centers) in the NW. These notches can be fabricated either by using nano-indentation or by a focussed ion beam. 2. To investigate whether DWs in different parts of the nanowire exhibit spatio-temporal correlation, a simultaneous detection of DWkinetics (through noise measurement) between different volage probes needs to be done. If the propagation time of DWs scales with the distance between the voltage probes, we can be confident of our velocity measurement. Then, by recording the DWvelocity as function of eld/current for nanowire (or nanostrip) absence (or presence) of the Walker breakdown can be probed. This would be a significant result for future spintronic devices. With an accurate determination of velocity even non- adiabaticity parameter may be calculated and one can see its effect on DW dynamics. 3. A complete understanding of sustained avalanches at finite magnetic fields, characterized by a high spectral exponent (a>¸ 2:5) in an ensemble of nanowires is still lacking. Per- forming a controlled experiment on a single nanowire, by varying the number of nanowires in the alumina matrix, one can study the chaotic dynamics of DWs in the ensemble in very accurate manner. All the experiments on AgNWs were performed on ensembles. The large change in a as well as noise magnitude in hcp AgNWs could arise from stress relaxation due to the presence of an insulating matrix or structural relaxation, determined by the nanowire growth kinetics. To resolve this issue, time and temperature dependent noise measurements should be performed on single nanowire stabilized in both hcp and fcc crystal structure.

Scanning probe microscopy was employed to characterize the piezotronic effect in both longitudinal and transverse force sensing modes in CdSe, and GaN nanowires, respectively. Both experimental results show exponential response of their conductivity change to applied forces. Theoretical models are also presented to explain this mechanism and quantify the relationship, where strain induced piezoelectric polarization changes the metal-semiconductor Schottky barrier height. An in-situ method based on SPM is developed to characterize the triboelectric process, including tribo-charge intensity, multi-cycle friction effect, as well as its surface diffusion. Beyond that, effect of external electric field was investigated as an approach to manipulate the polarization and intensity. Finally, a concept of self-powered motion sensing technology is developed and demonstrated experimentally with nanometer resolution, long working distance as well as high robustness. It provides a promising solution for application areas that need ultra-low power consumption devices.

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Zinc oxide is a semiconducting material that has received lot of attention due to its numerous proeprties such as wide direct band gap, piezoelectricity, and numerous low cost and robust methods of synthesizing nanomaterials. Its piezoelectric properties have been harnessed for use in energy production through nanogenerators, and to tune carrier transport, birthing a field known as piezotronics. However, one weakness of ZnO is that it is notoriously difficult to dope p-type. Antimony was investigated as a p-type dopant for ZnO, and found to have a stability of up to 3 years, which is completely unprecedented in the literature. Furthermore, a variety of zinc oxide structures ranging from ultra-long nanowires to thin films were produced and their piezotronic properties were demonstrated. By making p-n homojunctions using doped and undoped ZnO, enhanced nanogenerators were produced which could see application in gesture recognition. As a proof of concept, a simple photodetector was also derived from a core-shell nanowire structure. Finally, the ability to integrate this material with other semiconductors was demonstrated by growing a heterojunction with silicon nanowires, and investigating its electrical properties. All this work together lays the foundation for a fundamentally new material that could see application in future electronics, optoelectronics, and human-machine interfacing.

Nanomaterials such as gold nanowires and gold nanoparticles were self-assembled with several peptides derived from betaamyloid peptide. The peptides propensity to form fibrilar structures was exploited. The products obtained by aggregation of the peptides with the nano materials were studied using HPLC, UV-vis spectroscopy, TEM and optical light microscopy.

A research report submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfillment of the requirements for the degree of Master of Science. Johannesburg, 2015. / In this thesis electron transport properties of silicon nanowires are studied. The devices are synthesized using a laser ablation technique. The catalysts used in the synthesis are nickel nanoparticles. The silicon nanowires are characterized by scanning electron microscopy, transmission electron microscopy, atomic force microscopy and Raman spectroscopy. Dielectrophoresis is used to align and contact nanowires across two electrodes to create two-terminal devices. In addition four-terminal devices are fabricated using PMMA lift-off based electron beam lithography. Electron transport properties of the fabricated devices have been studied using dc measurement techniques. Resistance of the silicon nanowires has been measured as a function of temperature and magnetic field. These measurements have been accomplished using a Cryogenics system at low temperature, and high magnetic field. Temperature dependent studies reveal that Arrhenius type thermally activated transport behavior is the dominant transport mechanism in measurements at zero magnetic field. Magnetic field dependent measurements show a weak positive linear magnetoresistance. There are also strong oscillations in magnetoresistance curves. The temperature and field independence of the oscillations has been attributed to quantum interference effects.

Although the terrestrial flux of solar energy is enough to support human endeavors, storage of solar energy remains a significant challenge to large-scale implementation of solar energy production. One route to energy storage involves the capture and conversion of sunlight to chemical species such as molecular hydrogen and oxygen via water splitting devices. The oxygen evolution half-reaction particularly suffers from large kinetic overpotentials. Additionally, a photoactive material that exhibits stability in oxidizing conditions present during oxygen evolution represents a unique challenge for devices. These concerns can be potentially addressed with a metal oxide photoanode coupled with efficient water oxidation electrocatalysts. Despite decades of research, structure-composition to property relationships are still needed for the design of metal oxide oxygen evolution materials. This dissertation investigates transition metal oxide materials for the oxygen evolution portion of water splitting devices. Chapter I introduces key challenges for solar driven water splitting. Chapter II elucidates the growth mechanism of tungsten oxide (WOX) nanowires (NWs), a proposed photoanode material for water splitting. Key findings include (1) a planar defect-driven pseudo-one-dimensional growth mechanism and (2) morphological control through the supersaturation of vapor precursors. Result 1 is significant as it illustrates that common vapor-phase syntheses of WOX NWs depend on the formation of planar defects through NWs, which necessitates reconsideration of WOX as a photoanode. Chapter III presents work towards (1) single crystal WOX synthesis and characterization and (2) WOX NW device fabrication. Chapter IV makes use of the key result that WOX NWs are defect rich and therefore conductive in order to utilize them as a catalyst scaffold for oxygen evolution in acidic media. Work towards utilizing NW scaffolds include key results such as stability under anodic potentials and strongly acidic conditions used for oxygen evolution. Chapter V includes work characterizing nickel oxide/oxyhydroxide oxygen evolution catalysts at near-neutral pH. Key findings include (1) previous reports of anodic conditioning resulting in greater catalytic activity are actually due to incidental incorporation of iron impurities from solution and (2) through intentional iron incorporation via electrochemical co-deposition, catalytic activity is increased ~50-fold over Fe-free catalysts. This dissertation contains previously published coauthored material.