Metal oxides exhibit a wide range of chemical and electronic properties, making them an extremely interesting subject for numerous applications in modern electronics. The primary goal of this research is to develop metal-oxide-based electronic devices, including thin-film transistors (TFTs), resistance random-access memory (RRAM) and planar nano-devices. This research requires different processing techniques, novel device design concepts and optimisation of materials and devices. The first experiments were carried out to optimise the properties of zinc oxide (ZnO) semiconductors, in particular the carrier concentration, which determines the threshold voltage of the TFTs. Thermal annealing is one common method to affect carrier concentration and most work in the literature reports performing this process in a single-gas environment. In this work, however, annealing was carried out in a combination of air and nitrogen, and it was found that the threshold voltage could be tuned over a wide range of pre-determined values.Further experiments were undertaken to enhance the carrier mobility of ZnO TFTs, which is the most important material quality parameter. By optimising deposition conditions and incorporating a high-k gate dielectric layer, the devices showed saturation mobility values over 50 cm2/Vs at a low operating voltage of 4 V. This is, to our knowledge, one of the highest field-effect mobility values achieved in ZnO-based TFTs by room temperature sputtering. As an important type of metal-oxide-based novel memory devices, which have been studied intensively in the last few years, RRAM devices were also explored. New materials, such as tin oxide (SnOx), were tested, exhibiting bipolar-switching operations and a relatively large resistance ratio. As a novel process variation, anodisation was performed, which yielded less impressive results than SnOx, but with a potential for ultra-low-cost manufacturing. Finally, novel planar nano-devices were explored, which have much simpler structures than conventional multi-layered transistors and diodes. Three types of ZnO-based nano-devices (a side-gated transistor, a self-switching diode and a planar inverter) were fabricated using both e-beam lithography and chemical wet etching. After optimisation of the challenging wet etching procedure at nanometre scale, ZnO nano-devices with good reproducibility and reliability have been demonstrated.

Nano structured wide band gap semiconductors have attracted attention of many researchers due to their potential electronic and optoelectronic applications. In this thesis, we report successful synthesis of well aligned Eu doped ZnO nano-rods prepared, for the first time to our knowledge, by pulsed laser deposition (PLD) without any catalyst. X-ray diffraction (XRD) patterns shows that these Eu doped ZnO nanorods are grown along the c-axis of ZnO wurtzite structure. We have studied the effect of the PLD growth conditions on forming vertically aligned Eu doped ZnO nanorods. The structural properties of the material are investigated using a -scanning electron microscope (SEM). The PLD parameters must be carefully controlled in order to obtain c-axis oriented ZnO nanorods on sapphire substrates, without the use of any catalyst. The experiments conducted in order to identify the optimal growth conditions confirmed that, by adjusting the target-substrate distance, substrate temperature, laser energy and deposition duration, the nanorod size could be successfully controlled. Most importantly, the results indicated that the photoluminescence (PL) properties reflect the quality of the ZnO nanorods. These parameters can change the material’s structure from one-dimensional to two-dimensional however the laser energy and frequency affect the size and the height of the nanorods; the xygen pressure changes the density of the nanorods.

ZnO hat wegen seiner potenziellen Anwendung in elektronischen Geräten und als Katalysator viel Aufmerksamkeit erhalten. Die Struktur und Reaktivität von ZnO-Oberflächen haben eine direkte Bedeutung für die Leistung und Funktionalität dieser Geräte. Daher ist die Definition und das Verständnis der atomistischen Details von ZnO-Oberflächenstrukturen von besonderer Bedeutung. Die atomistischen Details von ZnO-Oberflächen hängen von den Präparationsverfahren ab. Nach der Kristallpräparation ist es notwendig, eine Oberflächencharakterisierung durchzuführen, um eine Verbesserung der Funktionalität und Effizienz von ZnO-basierten opto-elektronischen Bauelementen und Katalysatoren zu erreichen. Die atomistische Wahrnehmung der Reaktion zwischen einem organischen Molekül und ZnO-Oberflächen spielt eine entscheidende Rolle bei der Optimierung der Wasserstoff-on-demand-Lieferung in Brennstoffzellen. Das Verständnis der atomistischen Details von Adsorption, Diffusion und Dissoziation eines organischen Moleküls ebnet den Weg, um die Vorgänge bei der Wasserstofffreisetzung für Brennstoffzellen zu enträtseln. Mit dem Ziel, die Struktur- und Stöchiometriebestimmung mit Hilfe der XPS zu ermöglichen, präsentiere ich in dieser Arbeit die Ergebnisse einer umfassenden theoretischen Studie über die Kernniveauverschiebungen von ZnO-Oberflächenrekonstruktionen. Darüber hinaus biete ich eine gründliche Untersuchung der gemischt-terminierten Oberfläche, indem ich zunächst die Bedingungen untersuche, unter denen sich Methanol-Monolagen auf dieser Kristallfläche bilden können, und dann alle möglichen Wege für deren Reaktion erforsche. Diese Studie liefert ein umfassendes Bild, um die wahrscheinlichsten Reaktionsschritte zu identifizieren, die zur Interpretation der experimentellen Ergebnisse herangezogen werden können. Sie wird zukünftigen theoretischen Studien für ähnliche Reaktionen wie die Dehydrierung und die Kinetik der Monolagenbildung, die hier untersucht wurden, helfen. / Zinc-Oxide (ZnO) has been getting much attention over the past decades because of its potential application in electronic devices and as a catalyst. The structure and reactivity of ZnO surfaces have direct relevance for the performance and functionality of these devices. Therefore, defining and understanding the atomistic details of ZnO surface structures is of particular importance. The atomistic details of ZnO surfaces depend on the preparation procedures. After the crystal preparation, it is necessary to perform a surface characterization, to achieve an improvement in the functionality and efficiency of ZnO-based opto-electronic devices and catalysts. The atomistic perception of the reaction between an organic molecule and ZnO surfaces plays a crucial role in optimizing hydrogen-on-demand delivery in fuel cells, and understanding the atomistic details of adsorption, diffusion, and dissociation of a simple organic molecule paves the way towards unraveling the procedures involved in the hydrogen liberation for fuel cells. In this work, with the aim of enabling structure and stoichiometry determination by using X-ray photoelectron spectroscopy, I present the results of a comprehensive theoretical study on the core-level shifts of ZnO surface reconstructions. Moreover, I provide a thorough investigation of the mixed-terminated (10-10) surface by first examining the conditions under which methanol monolayers can form on this crystal face and by then exploring all possible pathways for its adsorption, diffusion, and initial dehydrogenation. This study provides a comprehensive picture to identify the most probable reaction steps that can be used to interpret experimental findings and will help future theoretical studies for reactions similar to dehydrogenation of organic molecules and monolayer-formation kinetics that were studied here.

Les matériaux composites peuvent présenter des propriétés qu'aucun des composants individuels ne présente. En outre, à l'échelle du nanomètre les nanocomposites peuvent présenter de nouvelles propriétés par rapport à l'état massif ou à des macrocomposites des mêmes composants en raison d’effets de confinement et d’effets quantiques liés à la taille. Les nanocomposites semi-conducteur/métal sont très intéressants en raison de leurs uniques propriétés catalytiques et opto-électroniques et la possibilité de les ajuster facilement. Ce travail de thèse étudie les interactions spécifiques et les propriétés physiques qui se manifestent dans les films minces de ZnO et nanocomposites ZnO-Au synthétisés par pulvérisation magnétron réactive continue. Premièrement, il est observé qu’il est possible d'ajuster les propriétés microstructurales et optiques des couches de ZnO en réglant les paramètres expérimentaux. La croissance épitaxiale de ZnO sur saphir a été réalisée pour la première fois dans des conditions riches en oxygène sans assistance thermique. En outre, une étude des propriétés optiques met en évidence la relation étroite entre les propriétés optiques et de la chimie des défauts dans les couches minces de ZnO. Un modèle a été proposé pour expliquer la grande dispersion des valeurs de gap rencontrées dans la littérature. Deuxièmement, il a été possible de révéler l'influence profonde de l'incorporation de l'or dans la matrice de ZnO sur des propriétés importantes dans des films nanocomposites. En outre, la présence de défauts donneurs (accepteurs) au sein de la matrice ZnO se permet de réduire (oxyder) les nanoparticules d’or. Ce travail de recherche contribue à une meilleure compréhension des nanocomposites semi-conducteurs/métal et révèle le rôle important de l'état de la matrice semi-conductrice et de la surface des particules pour les propriétés finales du matériau / Composite materials can exhibit properties that none of the individual components show. Moreover, composites at the nanoscale can present new properties compared to the bulk state or to macro-composites due to confinement and quantum size effects. The semiconductor/metal nanocomposites are highly interesting due to their unique catalytic and optoelectronic properties and the possibility to tune them easily. This PhD work gives insight into the specific interactions and resulting physical properties occurring in ZnO and ZnO-Au nanocomposite films grown by reactive DC magnetron sputtering. The results can be summarized in two points: First, it was possible to tune the microstructural and optical properties of ZnO. Epitaxial growth of ZnO onto sapphire was achieved for the first time in O2-rich conditions without thermal assistance. Also, a study of the optical properties highlights the close relationship between the bandgap energy (E_g ) and the defect chemistry in ZnO films. A model was proposed to explain the large scatter of the E_g values reported in the literature. Second, the deep influence of the incorporation of gold into the ZnO matrix on important material properties was revealed. Moreover, the presence of donor (acceptor) defects in the matrix is found to give rise to the reduction (oxidation) of the Au nanoparticles. This research work contributes to a better understanding of semiconductor/metal nanocomposites revealing the key role of the state of the semiconductor matrix

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The increasing prevalence of glass windows in modern buildings has raised the demand for solar control windows that possess climate-appropriate properties. Glass windows made of abundant and low-cost materials which can both decrease the heating energy consumption as well as enhance the light climate indoors would sufficiently meet the goals of economical yet uplifting buildings. The main objective of this thesis was to examine whether a plasmonic hybrid interface, comprising three layers of thin films (gold nanoparticles of approximately 10 nm, ZrO2 with a thickness range of 20-35 nm, and ZnO with a thickness of approximately 20 nm), could achieve the upconversion of infrared light to visible light through a multiphoton absorption process in the ZnO layer. If successful, this configuration, in conjunction with an established layer capable of downconverting ultraviolet light to visible light, would be applied to commercially available glass windows to enhance the solar utilization and improve indoor lighting conditions. ZnO was selected as the upconversion material due to its wide emission range in the visible spectrum, indicative of intermediate electron states between the valence and conduction bands suitable for excitation. The objective of the plasmonic material, the gold nanoparticles, was to increase the probability of the upconversion process by utilizing the enhanced electric field resulting from plasmons localized at the surface of the gold nanoparticles. ZrO2 served as a separator layer between the plasmonic material and the ZnO, to effectively preventing charge transfer and ensuring that any upconversion or other photoluminescence processes were purely photonic. Various optical experimental techniques were employed in this study to assess any upconversion, plasmon enhancement, and map the intermediate electron states of the ZnO. The ZrO2 layer successfully prevented charge transfer between the layers. However, the influence ofthe gold’s surface plasmons and it’s enhanced electric field on ZnO emission varied among the samples, likely due to the synthesis processes. Ultimately, the plasmonic hybrid interface investigated in this thesis did not exhibit detectable upconversion when illuminated with either 600 or 750 nm light. Further research is necessary to increase the density of intermediate electron states in ZnO, along with optimization of the thin film synthesis to enhance plasmon effects. These advancements would augment the probability of detectable upconversion.

Corrosion in underground and submerged steel pipes is a global problem. Coatings serve as an impermeable barrier or a sacrificial element to the transport of corrosive fluids. When this barrier fails, corrosion in the metal initiates. There is a critical need for sensors at the metal/coating interface as an early alert system. Current options utilize metal sensors, leading to accelerating corrosion. In this dissertation, a non-conductive sensor textile as a viable solution was investigated. For this purpose, non-woven zinc (II) oxide-polyvinylidene fluoride (ZnO-PVDF) nanocomposite fiber textiles were prepared in a range of weight fractions (1%, 3%, and 5% ZnO) and placed at the coating/steel interface. Electrochemical impedance spectroscopy (EIS) testing was performed during the immersion of the coated samples to validate the effectiveness of the sensor textile. In the second part of this dissertation, an accelerated thermal cyclic method has been applied to determine sensor's reliability in detecting corrosion under actual service condition. The results suggested that the coating is capable of detecting corrosion under harsh conditions. Moreover, the addition of ZnO decreases the error in sensor textile and improved coating's barrier property. In the next phase, experiments were conducted to detect the type of corrosion (pitting or uniform) underneath the protective coating as it has profound effect on overall performance and durability of the steel pipe. The data suggested that the pitting corrosion drew a lot of current, hence its resistance was significantly low which was tacked by the sensor accurately whereas the uniformly corroded specimens showed almost identical results which portrayed the sensor's ability to detect pitting corrosion.

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