The need for green and renewable fuels has led to the investigation of ways to exploit renewable resources. Solar among all the renewables is the most powerful and its conversion into usable energy would help in solving the energy problem our society is facing. Photocatalytic water splitting for hydrogen production is an example of solar energy storage into chemical bonds. The hydrogen produced in this way can then be employed as carbon free fuel creating the “Hydrogen Cycle”. This work investigates the structure and the activity of graphitic carbon nitride (g-C₃N₄), an organic semiconductor that proved a suitable photocatalyst for hydrogen production from water. Synthesised by thermal polycondensation of melamine it is a graphitic like material with a band gap of 2.7 eV which makes it a visible light active catalyst. In a first instance the effect of the synthesis conditions on its structure and morphology are investigated to find the optimum parameters. The temperature of condensation is varied from 450°C up to 650°C and the length from 2.5 h to 15 h. The structural changes are monitored via X-ray diffraction (XRD) and elemental analysis while the effect on the morphology and the band gap of g-C₃N₄ are investigated by mean of scanning electron microscopy and UV-Vis absorption. Subsequently, a study of the crystal structure of the catalyst is carried out. Using structures proposed in the literature, X-ray diffraction and neutron scattering simulations are used to narrow down the number of possible 3D structures. After structural characterisation, the activity of g-C₃N₄ for photocatalytic hydrogen evolution is evaluated. It is confirmed that loading 1 wt.% Pt on its surface significantly increases the hydrogen evolution rate. The attention then focuses on the loading procedures, the reduction pre treatments of the co-catalyst and the reasons of the different performances when different procedures are employed. The catalytic system is characterised by mean of X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and XRD. By investigating the composition and the morphology of the platinum nanoparticles under different conditions, the main factors responsible for the changes in activity of g-C₃N₄ for hydrogen evolution are identified. Additionally, the role of the co catalyst and its interaction with g-C₃N₄ is also elucidated. Finally, taking forward the knowledge acquired on the Pt-g-C₃N₄ system, the effect on the hydrogen evolution rate of alloying platinum with a second metal (Cu, Ag, Ni and Co) is studied. The nanoparticles are characterised by XRD and TEM. A screening of the loading procedures and bimetallic systems is performed to identify the most promising for photocatalytic hydrogen evolution with the aim of bringing them towards further investigation.

This study details the dielectrophoretic assembly and mechanical characterization of boron nitride nanotubes on silicon chips with gold electrodes. The chips were fabricated from 4in round silicon wafers with a 100nm-thick low stress silicon nitride insulating layer on the top and bottom. The electrodes were patterned using photo- and electron-beam lithography and dry etching, and the wafers were cut into 4 x 6mm chips. The boron nitride nanotubes studied were obtained from NIA and were synthesized via a unique pressurized vapor/condensor method, which produced long, small-diameter BNNTs without the use of a catalyst. These nanotubes were studied due to their desirable mechanical and electrical properties, which allow for unique applications in various areas of science, engineering, and technology. Applications span from magnetic manipulation to the formation of biocomposites, from nano-transistors to humidity and pH sensors, and from MRI contrast agents to drug delivery. The nanotubes and nanotube bundles characterized were suspended over gaps of 300 to 500nm. This study was unique in that assembly was performed using dielectrophoresis, allowing for batch fabrication of chips and devices. Also, stiffness measurements were performed using AFM, eliminating the reliance of other methods upon electron microscopes, and allowing for imaging and measurements to occur simultaneously and at high resolution. It was found that DEP parameters of V = 2.0Vpp, f = 1kHz, and t = 2min provided the best results for mechanical testing. The nanotubes tested had suspended lengths of 300nm, the width of the electrode gap, and diameters of 15–65nm. Chips were imaged with both scanning electron microscopy and atomic force microscopy. Force-displacement measurements with atomic force microscopy were used to find stiffness values in the range of 1–16N/m. These stiffness values, when plugged into a simple double-clamped beam model, indicated Young’s moduli of approximately 1–1600GPa. Within this wide range, it was shown that a decrease in diameter strongly correlated exponentially to an increase in Young’s modulus. Work in this study was divided between assembly and characterization. Therefore, a lot of time was spent working to optimize dielectrophoresis parameters, followed by SEM and AFM imaging. Parameters that were adjusted included DEP voltage and time, pre-DEP sonication times, as well as adding a centrifuging procedure to attempt to better separate nanotube bundles in solution. Another method discussed but not pursued was the use of surfactants to agitate the solution, thus separating the nanotubes. The reason this material in particular was so difficult to separate was twofold. First, the small size of the nanotubes—individual BNNTs have diameters on the order of ∼5 nanometers—generates very strong nanoscale van der Waals forces holding the nanotubes together. Larger nanotubes—with diameters on the order of 50 to 100nm or more—suffer less from this problem. Also, the dipoles created by the boron-nitrogen bonds cause attraction between adjacent nanotubes. The results shown in this thesis include DEP parameters, SEM and AFM images, and force- displacement curves leading to nanotube stiffness and Young’s modulus values. The force-displacement tests via AFM are also detailed and explained.

Master of Science / Department of Mechanical and Nuclear Engineering / Jeffrey Geuther / William L. Dunn / The properties of hexagonal boron nitride (h-BN) as a semiconductor neutron detection medium were investigated. Single h-BN crystal domains were synthesized by the Chemical Engineering department at Kansas State University (KSU) using crystallization from molten metal solutions. At Texas Tech University (TTU), a detector was fabricated using epitaxial h-BN growth on a sapphire substrate where metallic micro-strip contacts 5 [mu]m apart and 5 nm thick where deposited onto the un-doped h-BN. In this research both the crystal domains synthesized at KSU and the detector fabricated at TTU were tested for neutron response. Neutron irradiation damage/effects were studied in pyrolytic h-BN by placing samples in the central thimble of the TRIGA MARK II reactor at KSU and irradiating at increasing neutron fluences. The domains synthesized at KSU as well as the detector fabricated at TTU showed no response to neutron activity on a MCA pulse height spectrum. Conductivity analysis showed abrupt increases in the conductivity of the pyrolytic h-BN at around a fluence of 10[superscript]1[superscript]4 neutrons per cm[superscript]2. Bandgap analysis by photoluminescence on the irradiated pyrolytic h-BN samples showed shifts in energy due to towards plane stacking disorders upon neutron irradiation. Future efforts may include the introduction of dopants in h-BN growth techniques for charge carrier transport improvement, and mitigation of plane stacking disorders.

Master of Science / Department of Electrical and Computer Engineering / Behrooz Mirafzal / Wide bandgap devices have gained increasing attention in the market of power electronics for their ability to perform even in harsh environments. The high voltage blocking and high temperature withstanding capabilities make them outperform existing Silicon devices. They are expected to find places in future traction systems, electric vehicles, LED lightning and renewable energy engineering systems. In spite of several other advantages later mentioned in this paper, WBG devices also face a few challenges which need to be addressed before they can be applied in large scale in industries. Electromagnetic interference and new requirements in packaging methods are some of the challenges being faced by WBG devices. After the commercialization of these devices, many experiments are being carried out to understand and validate their abilities and drawbacks. This paper summarizes the experimental results of various applications of mainly Silicon Carbide (SiC) and Gallium Nitride (GaN) power devices and also includes a section explaining the current challenges for their employment and improvements being made to overcome them.

Doctor of Philosophy / Department of Chemical Engineering / Vikas Berry / Nanoscale materials invite immense interest from diverse scientific disciplines as these provide access to precisely understand the physical world at their most fundamental atomic level. In concert with this aim of enhancing our understanding of the fundamental behavior at nanoscale, this dissertation presents research on three nanomaterials: Gold nanoparticles (GNPs), Graphene and ultra-thin Boron Nitride sheets (UTBNSs). The three-fold goals which drive this research are: incorporating mobility in nanoparticle based single-electron junction constructs, developing effective strategies to functionalize graphene with nano-forms of metal, and exfoliating ultrathin sheets of Boron Nitride. Gold nanoparticle based electronic constructs can achieve a new degree of operational freedom if nanoscale mobility is incorporated in their design. We achieved such a nano-electromechanical construct by incorporating elastic polymer molecules between GNPs to form 2-dimensional (2-D) molecular junctions which show a nanoscale reversible motion on applying macro scale forces. This GNP-polymer assembly works like a molecular spring opening avenues to maneuver nano components and store energy at nano-scale. Graphene is the first isolated nanomaterial that displays single-atom thickness. It exhibits quantum confinement that enables it to possess a unique combination of fascinating electronic, optical, and mechanical properties. Modifying the surface of graphene is extremely significant to enable its incorporation into applications of interest. We demonstrated the ability of chemically modified graphene sheets to act as GNP stabilizing templates in solution, and utilized this to process GNP composites of graphene. We discovered that GNPs synthesized by chemical or microwave reduction stabilize on graphene-oxide sheets to form snow-flake morphologies and bare-surfaces respectively. These hybrid nano constructs were extensively studied to understand the effect and nature of GNPs’ interaction with graphene, and applied to address the challenge of dispersing bare-surfaced GNPs for efficient liquid-phase catalysis. We also revisited the functionalization of graphene and present a non-invasive surface introduction of interfaceable moieties. Isostructural to graphene, ultrathin BN sheet is another atomic-thick nanomaterial possessing a highly diverse set of properties inconceivable from graphene. Exfoliating UTBNSs has been challenging due to their exceptional intersheet-bonding and chemical-inertness. To develop applications of BN monolayers and evolve research, a facile lab-scale approach was desired that can produce processable dispersions of BN monolayers. We demonstrated a novel chlorosulfonic acid based treatment that resulted in protonation assisted layer-by-layer exfoliation of BN monolayers with highest reported yields till date. Further, the BN monolayers exhibited extensively protonated N centers, which are utilized for chemically interfacing GNPs, demonstrating their ability to act as excellent nano-templates. The scientific details obtained from the research shown here will significantly support current research activities and greatly impact their future applications. Our research findings have been published in ACS Nano, Small, Journal of Physical Chemistry Letters, MRS Proceedings and have gathered >45 citations.

Le nitrure de bore hexagonal (h-BN) est un semi-conducteur à large bande interdite (~ 6 eV) avec une stabilité thermique et chimique très élevées lui offrant la possibilité d'être utilisé dans des dispositifs fonctionnant dans des conditions de fonctionnements extrêmes. La nature indirecte de la bande interdite dans h-BN a été étudiée à la fois par des calculs théoriques et par des expériences. Un exciton indirect et des recombinaisons assistées par phonons dans h-BN ont été observées par photoluminescence.Durant cette thèse, nous avons étudié les propriétés optiques de cristaux massifs et de couches hétéro-épitaxiales de nitrure de bore hexagonal. Nous avons étudié des échantillons provenant de différentes sources et des cristaux qui ont été fabriqués en utilisant différentes méthodes de croissance pour nous permettre de mesurer les propriétés optiques intrinsèques de h-BN. Nous rapportons l'impact des symétries des phonons sur la réponse optique du h-BN en effectuant des mesures photoluminescence résolues par polarisation. L’analyse des données en polarisation, nous permet de mesurer la contribution du phonon manquant, celui qui n'a pas été détectée avant cette thèse. En suite, nous démontrons que l'origine de la structure fine du spectre de PL provient pour chaque réplique phonon d’une diffusion complémentaire de type Raman faisant intervenir le mode de phonon E2g à basse énergie (mode de cisaillement inter-feuillets). Les spectroscopies de photoluminescence et de diffusion inélastique Raman ont été combinées pour quantifier l'influence des effets isotopiques sur les propriétés optiques de h-BN ainsi pour révéler que les modifications des interactions de van de Waals liées à l'utilisation de 10B et 11B ou du bore naturel pour la croissance de cristaux h-BN massifs.Enfin, nous étudions des epitaxis de h-BN crues par Épitaxie sous Jets Moléculaires. L'utilisation conjointe de l’imagerie par microscopie à force atomique (AFM) et de la spectroscopie de photoluminescence permet de comprendre la première observation de recombinaison assistée par phonons dans des épitaxies de h-BN sur le saphir et le graphite. Ce résultat indique que la croissance de h-BN à large échelle par méthode épitaxiales est en voie d'acquérir la maturité nécessaire au développement technologique de h-BN. / Hexagonal boron nitride (h-BN) is a wide bandgap (~ 6 eV) semiconductor with a very high thermal and chemical stability often used in devices operating under extreme conditions. The indirect nature of the bandgap in h-BN is investigated by both theoretical calculations and experiments. An indirect excion and phonon-assisted reombinations in h-BN are observed in photoluminescene spectroscopy.This thesis focus on the optical properties of bulk and epilayers of h-BN. We investigated samples from different sources grown different methods in order to confirm the intrinsic optical properties of h-BN. We report the impact of the phonon symmetry on the optical response of h-BN by performing polarization-resolved PL measurements. From them, we will measure the contribution of all the phonon-assisted recombination which was not detected before this thesis. We follow by addressing the origin of the fine structure of the phonon-assisted recombinations in h-BN. It arises from overtones involving up to six low-energy interlayer shear phonon modes, with a characteristic energy of about 6.8 meV.Raman and photoluminescence measurements are recorded to quantify the influence of isotope effects on optical properties of h-BN as well as the modifications of van de Waals interactions linked to utilization of 10B and 11B or natural Boron for the growth of bulk h-BN crystals.Finally, we study h-BN thin epilayers grown by Molecular Beam Epitaxy at Nottingham University, atomic force microscopy (AFM) images and photoluminescence features are combined to confirm the first observation of phonon-assisted recombination in high quality thin h-BN epilayers grown on c-plane sapphire and Highly Ordered Pyrolitic Graphite. This demontrates that large scale growth of h-BN by epitaxy is getting a technologically required maturity.

Gallium Nitride (GaN) power devices have the potential to jump-start the next generation of power converters which are smaller, faster, denser, and cheaper. They are thus expected to meet the increasing 21st Century need for power density and efficiency, while at the same time reducing pollution. With the commercialisation of 600 V GaN power devices, which the industry is keen to adopt, come significant challenges. Since there are a number of such devices which are new to the power community, there is a steep learning curve involved, with dispersed information on how best to employ these devices. This work aims to solve this problem through the development of a universal GaN power device and circuit model and the formulation of design rules and guidelines. Through this contribution, designers will be able to better understand and work with these novel devices with relative ease. This will aid the need for faster adoption of GaN devices by the industry solving the barriers to commercialisation. This research demonstrates the use of machine learning (ML) algorithms for behavioural modelling of GaN power devices. Introducing ML as the key to developing a general behavioural and circuit model for GaN power devices combined with understanding, learning, customizing and successfully demonstrating it is the major contribution of this research work. This research first presents a comprehensive investigation into the parasitic effect on the GaN device switching performance. A simple process based on RF techniques is introduced to approximately extract the impedances of the GaN device to develop a behavioural model. The switching behaviour of the model is validated using simulation and double pulse test experiments at 450 V, 10 A test conditions. The developed behavioural model for Transhporm GaN HEMT is 95.2% accurate as the existing LT-spice manufacturer model, and is very much easier for power designers to handle, without the need for knowledge about the physics or geometry of the device. However, given that separate models would need to be developed for each commercial GaN device, the need for a generalized and accurate GaN behavioural model was identified, and it is this generalised model that the remainder of this thesis focuses on. In the next part of this research, a GaN platform test bench is built through bridging RF and power electronics design methodologies to achieve a gate loop and power loop inductance of around 1.8nH with switching waveforms with rise time and fall time around 2.5ns at 450V, 15A, 500KHz test conditions. The double pulse test circuits are customized using different off the shelf gate drives and analysed for collecting switching data for training the ML model. ML modelling using supervised learning is used to predict the switching voltage and current waveforms thus making it possible to construct a generic GaN black box model. Different architectures with single and multi- layer neural networks are explored for modelling. The ability to demonstrate a GaN device ML model that maps both voltage and current inputs and outputs is another characteristic and novel feature of this work. This research demonstrates different types of GaN ML models. The developed voltage and current prediction models are based on feed forward neural network (FFNN), long short-term memory unit (LSTM) and gated recurrent unit (GRU). Several parameters are quantified and compared for validating the models. They are the network architectures, parameters, training time, validation loss and error loss. The ML models are also compared with the demonstrated model of chapter 3 and existing LT-Spice manufacturer models. The results show that the author has been able to develop a GaN LSTM ML model with an error rate of 0.03, and convergence at 3s with excellent stability. The ML based modelling is then translated from GaN power devices to GaN based circuits. Among the different neural network architectures trained and tested, a multi FFNN with 5 hidden layers and 30 neurons, was found to be the best for prediction and optimization. The switching behaviour comparison results shows the benefits and value of ML modelling in opening up whole new possibilities of employing advanced control algorithms for very efficient, reliable and scalable performance of GaN power electronics systems. Finally, the findings of this work have been generalized to frame machine learning based techniques to address the need for generic modelling of power electronic devices. These solutions are presented as an information manual to researchers, engineers and students interested in benefiting from adopting machine learning for power electronics applications.

Filmes finos de nitreto de silício com excesso de nitrogênio foram depositados sobre silício por sputtering reativo para obter estruturas emissoras de luz. As amostras foram modificadas por implantação iônica para verificar a influência dos dopantes arsênio (As) e boro (B) nos espectros de fotoluminescência (PL). As medidas de PL foram realizadas na faixa de temperatura entre 15-300 K e apresentaram uma emissão entre os comprimentos de onda 370-870 nm. Os dopantes introduziram uma emissão em 725 nm na banda de emissão, principalmente as dopadas com As. Foram realizadas medidas de microscopias para verificar a presença de nanoestruturas assim como a distribuição dos dopantes no material. As imagens de microscopias confirmaram a presença de nanocristais de nitreto de silício nas fases α, β e γ e identificaram a presença do dopante B nas fases cristalinas. O modelo de condução de Pool-Frenkel domina o transporte de portadores, indicando que a condução ocorre pelos níveis intrabandas, característica que definiu o modo que as recombinações radiativas ocorreram. As medidas de eletroluminescência (EL) apresentaram uma emissão centrada nos comprimentos de onda 760 e 880 nm (polarização negativa) e 1010 nm (polarização positiva) revelando diferenças significativas quando comparadas com as medidas de PL. Essa diferença esta associada à maneira como os elétrons populam os níveis intrabanda (excitação óptica para PL e elétrica para EL) que resulta em recombinações radiativas em diferentes comprimentos de ondas. A intensidade dos espectros de EL manifestou uma dependência quase linear com a densidade de corrente para ambas as polarizações. As medidas de EL em campos alternados exibiram um espectro de emissão composto pela soma das bandas obtidas separadamente em cada uma das polarizações. Medidas de EL em diferentes temperaturas (50-300 K) foram realizadas para investigar a influência da temperatura nos processos de recombinação radiativa. A intensidade exibiu uma redução com o aumento da temperatura, devido ao aumento do acoplamento elétron-fônon. / Silicon nitride with excess of nitrogen thin films were deposited on silicon substrate by reactive sputtering in order to obtain light emitting structures. Samples were modified by ion implantation of arsenic (As) and boron (B) to ascertain dopant leverage at photoluminescence (PL) spectra. PL measurements were performed at temperature ranging from 15 K up to 300 K and showed a band emission between wavelength 370 and 870 nm. An emission centered at 725 nm was observed in doped samples; especially in the presence of As. Microscope images showed crystalline structures of α-Si3N4, β-Si3N4 and γ-Si3N4 and confirmed boron dopant in nanocrystalline structures. Pool-Frenkel conduction model dominates electron transport in non-stoichiometric silicon nitride films due to intraband levels, phenomenon that has a huge contribution to electroluminescence (EL) emission. EL signals were composed by two peaks centered at 760 and 880 nm (negative bias – EL-N) and one peak at 1010 nm (positive bias – EL-P). Diffences between PL and EL spectra exhibit a clear dependence on the mode of excitation (photo and current source) on radiative recombination process. EL intensity had almost a linear increase with current density for both polarizations. EL measurements under AC voltage were composed by a superposition of the signals from EL-N and EL-P signals. Photo and electroluminescence measurements were collected at different temperatures (50 to 300 K) in order to investigate the temperature influence on the radiative recombination. The EL intensity was decreasing with temperature increasing, due to electron-phonon interactions.

Graphene, since its first isolation, carries many promises on its superior properties. However, unlike its conventional two-dimensional (2D) counterparts, e.g. Si and GaAs systems, graphene represents the first 2D systems built on an atomically thin structure. With every atoms on the surface, graphene is severely affected by the environment and the measured properties have not reaching its full potential. Avoiding all possible external contamination sources is the key to keep graphene intact and to maintain its high quality electronic properties. To achieve this, it requires a revolution in the graphene device structure engineering, because all factors in a conventional process are scattering sources, i.e. substrate, solvent and polymer residues. With our recent two inventions, i.e. the van der Waals transfer method and the metal-graphene edge-contact, we managed to completely separate the layer assembly and metallization processes. Throughout the entire fabrication process, the graphene layer has never seen any external materials other than hexagonal boron nitride, a perfect substrate for graphene. Both optical and electrical characterizations show our device properties reach the theoretical limit, including low-temperature ballistic transport over distances longer than 20 micrometers, mobility larger than 1 million cm²/Vs at carrier density as high as 2 ×10^12 cm^-2, and room-temperature mobility comparable to the theoretical phonon-scattering limit. Moreover, for the first time, we demonstrate the post-fabrication cleaning treatments, annealing, is no longer necessary, which greatly eases integration with various substrate, such as CMOS wafers or flexible polymers, which can be damaged by excessive heating. Therefore the progress made in this work is extremely important in both fundamental physics and applications in high quality graphene electronic devices. Furthermore, our work also provides a new platform for the high quality heterostructures of the 2D material family.

In this thesis, optical studies of c-plane InGaN/GaN quantum well (QW) structures are presented. The effects of a Si-doped underlayer (UL) on the optical properties of multiple quantum well (MQW) structures are investigated. The QW photoluminescence (PL) emission peak energy and radiative recombination rate decrease and increase respectively with increasing number of QWs. These observations are attributed to the increasing net electric field across the MQW structure as the strength of the surface polarisation field, which acts in the opposite sense to the piezoelectric polarisation fields across the QWs, reduces with increasing distance of the UL from the sample surface. This leads to a reduction in the electron-hole recombination energy and wavefunction overlap. It is also shown that the internal quantum efficiency of the MQW structures may decrease with increasing number of QWs due to the reducing radiative recombination rate, which could indicate that carrier losses due to thermionic emission or interface recombination are mitigated by the inclusion of an UL. Optical studies of single QW structures containing Si-doped ULs with different net electric fields across the QW are presented. The net electric field across the QW is changed by varying the thickness of the GaN cap layer. The full width at half maximum of the emission peak increases with increasing net electric field across the QW. This is attributed to the increasing variation in electron ground state energies due to the role of the electric field in the localisation of electrons at quantum well width fluctuations. For one sample, a smaller Huang-Rhys factor compared to the rest of the samples is calculated. The non-exponential PL decays detected on the low energy side of the QW emission peak from this sample are also of a different shape to the other PL decays detected at all energies for the other samples. This may be due to the reversal of the net electric field across these QW regions. Observations of a broad emission band on the high energy side of single QW structures at high excited carrier densities are presented. This band occurs in the carrier density regime at which the efficiency droop is observed. The emission band is attributed to higher energy weakly localised or delocalised electron and hole states that are populated following the saturation of the localised ground states. PL decay curves detected across this emission band exhibit plateaus where the PL intensity remains constant until the higher energy emission has decayed. These are similar to decays observed in semiconductor quantum dots, which are characteristic of Pauli state blocking.