>Magister Scientiae - MSc / FeSi nanowires were synthesized via a chemical vapor deposition method. Anhydrous FeCl3 powder in this case served as the Fe source and was evaporated at a temperature of 1100oC to interact with silicon substrates which served as the silicon source. The nanowires followed the vapor solid (VS) growth mechanism, which does not require the use of a metal catalyst; the native silicon oxide layer on the silicon substrates played the role of the catalyst in the growth of these nanostructures. A second growth mechanism, involving the use of a metal catalyst to assist in the growth of the nanowires was attempted by depositing a thin film of gold on silicon substrates. The reaction yielded SiOx nanowires; these results are discussed in detail in Chapter 5. All the nanostructures were characterized by X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Photoluminescence Spectroscopy (PL), Raman Spectroscopy and Fourier Transform Infrared Spectroscopy (FTIR).

Les capteurs de gaz à base d'oxydes métalliques connaissent un engouement croissant pour des applications industrielles, militaires et environnementales. Néanmoins, ces capteurs se montrent peu sélectifs et nécessitent des températures de travail élevées pour obtenir une bonne sensibilité. La nanostructuration des matériaux permet d'augmenter la surface de réaction entre le gaz et le matériau hôte, améliorant ainsi la performance du capteur. ZnO est un semi-conducteur à large gap direct (3,37 eV) possédant de nombreuses propriétés physico-chimiques intéressantes, et aussi un matériau très prometteur pour les capteurs de gaz de type oxyde métallique. L'Elaboration de nanostructures de ZnO a conduit à un grand nombre d'études pour divers domaines d'applications. Dans ce contexte, cette thèse a pour objectif la synthèse des réseaux de nanofils de ZnO par voie hydrothermale et l'étude de leurs propriétés de détection. La première partie de ce travail porte sur l'étude systématique des différents paramètres influençant la synthèse des nanofils de ZnO. Les résultats montrent que la température de croissance, le pH de la solution et le temps de croissance influent sur la morphologie des nanofils de ZnO. Des nanofils avec un facteur d'aspect proche de 30 ont été obtenus sous conditions d'élaboration optimisées. La seconde partie de ce travail consiste en l'étude des propriétés de détection de nanofils de ZnO, par des méthodes électrique et optique. Les mesures électriques montrent une variation de résistance des nanofils, tandis que l'absorption UV révèle un déplacement du bandgap en présence du gaz. Une diminution de la résistance et un blue-shift de bandgap ont été observés lors de la présence d'un gaz réducteur tel que l'éthanol / Metal oxides based gas sensors are widely used in industrial, military and environmental applications. But the main fault of these sensors remains on their lack of selectivity and requiring high working temperature to obtain a good sensitivity. Nanostructuration of the materials presents an efficient way to enhance the reaction surface between gas and the host material, thus improving the sensor performance. ZnO is an n-type semiconductor with large bandgap energy of 3.37 eV at room temperature owning many interesting physical and chemical properties, and is also very sensitive for reducing gases. In recent years, many studies develop and improve the ZnO related nanostructures for various applications. The goal of this thesis consists in the synthesis of the ZnO nanowire arrays via hydrothermal method and the study of their sensing properties. The first part of this work shows a systematic study of the various influencing parameters during the ZnO nanowire synthesis. The results show that the growth temperature, the solution pH value and the growth time influence the nanowire morphology. Nanowires with an aspect ratio about 30 have been obtained under optimized growth conditions. The second part of this work consists of the study of the ZnO nanowire sensing properties, using both electrical and optical methods. The electrical measurements show a resistivity variation of the nanowires, while the UV absorption spectra reveal a bandgap shift under injected gas. A resistivity reduction and a blue-shift of a bandgap of the ZnO nanowires were observed under injected reducing gas such as ethanol

III-nitride nanowires (NWs) have been recognized as efficient photoelectrochemical (PEC) devices due to their large surface-to-volume ratio, tunable bandgap, and chemical stability. Doping engineering can help to enhance the PEC performance further. Therefore, addressing the effects of Si and Mg doping on the III-nitride NW photoelectrodes is of great interest. In this study, doping levels of NWs were tuned by the dopant effusion cell temperature of the molecular beam epitaxy (MBE) growth. The successful doping of the III-nitride NWs was confirmed using photoluminescence (PL), Raman spectroscopy, and open circuit potential (OCP) measurements. The ionized dopant concentrations of Si-doped InGaN/GaN NWs were systematically quantified by electrochemical impedance studies (EIS). Due to the three dimensional surfaces of NWs, modified Mott-Schottky formulas were induced to improve the accuracy of ionized dopant concentrations. The highest dopant concentration of Si-doped InGaN NWs can reach 2.1x1018 cm-3 at Tsi = 1120 oC. Accordingly, the estimated band edge potentials of the tested NWs straddled the redox potential of water splitting. The PEC performance of these devices was investigated by linear scan voltammetry (LSV), chronoamperometry tests, and gas evolution measurements. The results were consistent with the quantified dopant concentrations. The current density of n-InGaN NWs doped at TSi = 1120 oC was nine times higher than the undoped NWs. Additionally, the doped NWs exhibited stoichiometric hydrogen and oxygen evolution. By doping Mg into InGaN and GaN segments separately, the p-InGaN/p-GaN NWs demonstrated improved PEC performance, compared with undoped-InGaN/p-GaN and n-InGaN/n-GaN NWs. The p-InGaN/p-GaN NWs exhibited a highly stable current density at ~-9.4 mA/cm2 for over ten hours with steady gas evolution rates (~107 μmol/cm2/hr for H2) at near a stoichiometric ratio (H2: O2~ 1.8:1). This study demonstrated that optimizing the doping level and appropriate band engineering of III-nitride NWs is crucial for enhancing their PEC water splitting performance.

A conductive atomic force microscopy (c-AFM) investigation of GaN nanostructures is reported for strain engineering optoelectronic and piezotronic devices. The use of AFM enables the simultaneous correlation between the surface morphology and charge carrier transport through the nanostructures. The samples under investigation are molecular beam epitaxy (MBE) grown InGaN/GaN nanowires on Ti coated Mo substrate and GaN nanowires on ITO. The metal-semiconductor interface between the metallic substrates and the GaN nanostructures form the bottom contact. A Pt-Ir coated AFM probe is used to create a Schottky top nano-contact. The two interfaces form a metal-semiconductor-metal (MSM) structure. Force and temperature-dependent IV curves are obtained and analyzed, and the MSM structure parameters are extracted. Modulation of both the conductivity and Schottky barrier height (SBH) is revealed. Drastic reduction of the barrier is observed to drive the junctions to ideal MSM under a combination of force and temperature, revealing a dynamic and controlled two-way switching of the devices from rectifying to ideal linear IV properties. Through compressive force modulation by AFM tip, a symmetric 80 meV reduction in SBH at ±0.7 V is realized for the sample grown on Mo. By a combination of temperature and force modulation, a 40 meV increase in SBH is achieved at 0.53 V for the sample on ITO. These results show that the formed structure is ideal for applications in optoelectronics, sensing, piezotronic, piezo-phototronic, and nano-energy harvesting devices.

Mesenchymal stem cells (MSCs) are the most widely used source for bone tissue engineering due to their capability of multipotent differentiation. The use of nanotechnology in biomedical applications and therapy has increased in recent years provides an elegant alternative in comparison to current tissue engineering methods. Magnetic nanowires have a high potential in the medical field, as they are biocompatible, are simple to fabricate, possess low cytotoxic effects and can be operated wirelessly via magnetic fields. A nanowire substrate (NW) can provide a surface with tunable elastic properties. Therefore, magnetic nanowires have many promising applications such as in cell therapy, cell separation, cancer treatment, and as a scaffold for cell culture. This thesis explores the effects of alternating magnetic field (AMF) as a biophysical stimulator of osteogenic differentiation of MSCs by culturing the stem cells on a magnetic iron (Fe) NW. To this end, Fe nanowires were fabricated through electrodeposition and interactions between the NW and cells were analysed by electron microscopy. An AMF was applied to the NW in order to induce a vibration. MSCs were exposed to different magnetic field intensities, 250 mT and 50 mT, for different application times, 12 hours on followed by 12 hours off for two days and 24 hours on followed by 12 hours off. Differentiation was determined through the assessment of osteogenic markers at the mRNA level by RT-PCR and at the protein level by flow cytometry and fluorescence microscopy. Different effects were observed on MSCs grown on Fe NWs following exposure to different magnetic field intensities and duration applications. MSC differentiation towards the osteogenic lineage increased with increased field intensities. The most enhanced osteogenic differentiation of MSCs was observed at 250 mT AMF for 12 hours, as evidenced by elevated osteogenic markers at mRNA level compared to that of an AMF free control. Based on these results, we proposed that culturing MSCs on magnetic nanomaterials has the potential to control and promote osteogenesis under magnetic field and without the addition of external differentiation factors. These findings provide a new tool for stem cell research as an effective technology for bone tissue engineering and regenerative medicine.

Magnetic sensors are deployed in many applications such as automotive, consumer electronics, navigation and data storage devices. Their market’s growth is driven by demands of higher performance; primarily to assist in the advancement of the Internet of Things (IoT) and smart systems. Challenging obstacles of miniaturization and power consumptions must be overcome. A leading sensor that has the potential to accelerate the development is the magnetic tunnel junction (MTJ) devices. Corrosion causes catastrophic consequences for industries. Preventive measures could save up to 35% of annual corrosion-related costs. An advanced corrosion sensing technique is developed based on iron nanowires. The iron nanowires are magnets which lose their magnetization when corroded. Their magnetization loss is monitored using sensitive MTJ sensor. Combined, the nanowires and the MTJ sensor realize a highly integrated sensor concept that enables corrosion sensing with an ultra-low power consumption of less than 1 nW, a sensitivity of 0.1 %/min, a response time of 30 minutes and an area of 128 μm2. Surgical tool development is accelerating in the healthcare sector. Cardiac catheterization specifically is a minimally invasive surgery that relies heavily on x-ray imaging and contrast dyes. A flexible tri-axis MTJ sensor is developed to help minimizing the need for x-ray imaging during the procedure. The flexible sensor can bend to a diameter of 500 μm without compromising the performance and can endure over 1000 bending cycles without fatigue. Three flexible sensors are mounted onto the tip of a 3 mm cardiac catheter, realizing a novel sensor-on-tube (SOT) tri-axis sensor concept. The sensor has a high sensitivity of 9 Ω/° and an MR ratio of 29%. It weighs 16 μg only, adds 5 μm to the catheter’s diameter and a total size 300 μm2. The prototype system estimated the heading angle with an RMS error value of 7° and tracked the orientation of the sensor with an acceptable accuracy. However, the sensor has a misalignment issue caused by the manual placement of the sensors. A high precision tool is needed for the assembly, and any further misplacement -within a reasonable margin of error- could be corrected by calibration algorithms.

InGaN is a promising semiconductor for solid state lighting thanks to its bandgap which spans the entire visible regime of the electromagnetic spectrum. InGaN is grown heteroepitaxially due to the absence of a native substrate; however, this results in a strained film and a high dislocation density—two effects that have been associated with efficiency droop, which is the disastrous drop in efficiency of a light-emitting diode (LED) as the input current increases. Heteroepitaxially grown nanowires have recently attracted great interest due to their property of eliminating the detrimental effects of the lattice mismatch and the corollary efficiency droop. In this study, InGaN nanowires were grown on a low-cost Si (111) substrate via molecular beam epitaxy. Unique nanostructures, taking the form of mushrooms, have been observed in localized regions on the samples. These nanomushrooms consist of a nanowire body with a wide cap on top. Photoluminescence characterization revealed that the nanowires emit violet-blue, whilst the nanomushrooms emit a broad yellow-orange-red luminescence. The simultaneous emission from the nanowires and nanomushrooms forms white light. Structural characterization of a single nanomushroom via transmission electron microscopy revealed a simultaneous increase in indium and decrease in gallium at the interface between the body and the cap. Furthermore, the cap itself was found to be indium-rich, confirming it as the source of the longer wavelength yellow-orange-red luminescence. It is believed that the nanomushroom cap formed as a consequence of the saturation of growth on the c-plane of the nanowire. It is proposed that the formation of an indium droplet on the tip of the nanowire saturated growth on the c-plane, forcing the indium and gallium adatoms to incorporate on the sidewall m-planes instead, but only at the nanowire tip. This resulted in the formation of a mushroom-like cap on the tip. How and why the indium droplets formed is not entirely clear, but a localized temperature dip may have been the cause. Ultimately, the simultaneous growth of nanowires and nanomushrooms on the same substrate may pave the way to the development of a phosphor-free, efficient, inherent white LED.

Nanoscale materials are not new in either nature or physics. However, the recent technological improvements have given scientists new tools to understand and quantify phenomena that occur naturally due to quantum confinement effects. In general, these phenomena induce remarkable optical, magnetic, and electronic properties in nanoscale materials in contrast to their bulk counterpart. In addition, scientists have recently developed the necessary tools to control and exploit these properties in electronic devices, in particular field effect transistors, magnetic memories, and gas sensors. In the present thesis we implement theoretical and computational tools for analyzing the ground state and electronic transport properties of nanoscale materials and their performance in electronic devices. The ground state properties are studied within density functional theory using the SIESTA code, whereas the transport properties are investigated using the non-equilibrium Green's functions formalism implemented in the SMEAGOL code. First we study Si-based systems, as Si nanowires are believed to be important building blocks of the next generation of electronic devices. We derive the electron transport properties of Si nanowires connected to Au electrodes and their dependence on the nanowire growth direction, diameter, and length. At equilibrium Au-nanowire distance we find strong electronic coupling between electrodes and nanowire, resulting in low contact resistance. For the tunneling regime, the decay of the conductance with the nanowire length is rationalized using the complex band structure. The nanowires grown along the (110) direction show the smallest decay and the largest conductance and current. Due to the high spin coherence in Si, Si nanowires represent an interesting platform for spin devices. Therefore, we built a magnetic tunneling junction by connecting a (110) Si nanowire to ferromagnetic Fe electrodes. We have find a substantial low bias magnetoresistance of ~ 200%, which halves for an applied voltage of about 0.35 V and persist up to 1 V. In order to account for shallow impurities coming from bulk Si, the nanowire is doped with either P or B atoms (n or p type). Doping in general decreases the magnetoresistance as soon as the conductance is no longer dominated by tunneling. On the other hand, we study the electron transport properties of Si nanotubes connected to Au electrodes. The general properties turn out to be largely independent of the nanotube chirality, diameter, and length. However, the tunneling conductance of Si nanotubes is found to be significantly larger than in Si nanowires, while having a comparable band gap. For this reason we simulate a Si nanotube field effect transistor by applying an uniform potential gate. Our results demonstrate very high values of the transconductance, outperforming the best commercial Si field effect transistors, combined with low values of the subthreshold swing. Phosphorene (monolayer black P) is the only elemental two-dimensional material besides graphene that can be mechanically exfoliated and also can support electronics. Specific dislocations of the atoms in the phosphorene lattice generate another stable two-dimensional allotrope with buckled honeycomb lattice, blue P. We demonstrate structural stability of monolayer zigzag and armchair blue P nanotubes by means of molecular dynamics simulations. The vibrational spectrum and electronic band structure are determined and analyzed as functions of the tube diameter and axial strain. The nanotubes are found to be semiconductors with a sensitive indirect band gap that allows flexible tuning. We study the adsorption of CO, CO2, NH3, NO, and NO2 molecules on blue P nanotubes. They are found to surpass the gas sensing performance of other nanoscale materials. Investigations of the gas adsorption and induced charge transfer indicate that blue P nanotubes are highly sensitive to N-based molecules, in particular NO2, due to covalent bonding. The current-voltage characteristics of nanotubes connected to Au electrodes is used to evaluate the change in resistivity upon adsorption. The observed selectivity and sensitivity properties make blue P nanotubes superior gas sensors for a wide range of applications. Using black P and blue P nanoribbons, we configure field effect transistors with atomically perfect junctions by using armchair nanoribbons as semiconducting channel and zigzag nanoribbons as metallic leads. We characterize the devices and observe a performance superior to Si-based devices, with on/off ratio of ~ 103, low subthreshold swing of ~ 60 mV/decade, and high transconductance of ~ 104 S/m.

This thesis is a study of the structural, electrical and magnetic properties of indium antimonide (InSb) nanowires (NWs), that were synthesized by a template-assisted ordered growth technique via electrochemical deposition. InSb was chosen for this study because of its intrinsic properties that make it a material of choice for applications in high channel mobility, infrared (IR) sensing, thermoelectrics, and magnetoresistive sensing martials. This work has four main components: (i) Growth in commercially available anodic aluminum oxide (AAO) template, where hole-dominated conduction was observed, following NW growth in a low pH electrolyte. The challenge in using these AAO templates was in covering the back surface of the pores with a metal film. Uncovered pores resulted in electrolyte leakage and non-reproducible results. (ii) Growth in flexible polycarbonate membranes, where the flexibility of the membranes resulted in polycrystalline or high defect density NW growth. (iii) Fabrication of an AAO template, where the barrier layer thinning technique was found to be efficient in removal of the think aluminum oxide barrier that exists at the interface between the template and the aluminum metal. This allows for direct growth of NWs into the template pores without the need for metal evaporation. (iv) Fabrication of a heterostructure comprising of an InSb layer sandwiched between two ferromagnetic contacts. Preliminary results show evidence of inverse spin-valve effect at the low temperature of 4K.

Philosophiae Doctor - PhD / The rapid increase in global energy demand in recent decades coupled with the adverse environmental impact of conventional fuels has led to a high demand for alternative energy sources that are sustainable and efficient. Renewable solar energy technologies have received huge attention in recent decades with the aim of producing highly efficient, safe, flexible and robust solar cells to withstand harsh weather conditions. c-Si has been the material of choice in the development of conventional inorganic solar cells owing to it superior properties, abundance and higher efficiencies. However, the associated high costs of Si processing for solar cells have led to a gravitation towards alternative organic solar cells which are cheaper and easy to process even though they suffer from stability and durability challenges. In this work, combination of both inorganic and organic materials to form hybrid solar cells is one of the approaches adopted in order to address the challenges faced by solar cell development.