Electrical machine characterisation and analysis for renewable energy applications

There has been an increased use of the Doubly-Fed Induction Machine (DFIM) in ac drive applications in recent times, particularly in the field of renewable energy systems and other high power variable-speed drives. The DFIM is widely regarded as the optimal generation system for both onshore and offshore wind turbines and has also been considered in wave power applications. Wind power generation is the most mature renewable technology. However, wave energy has attracted a large interest recently as the potential for power extraction is very significant. Various wave energy converter (WEC) technologies currently exist with the oscillating water column (OWC) type converter being one of the most advanced. There are fundemental differences in the power profile of the pneumatic power supplied by the OWC WEC and that of a wind turbine and this causes significant challenges in the selection and rating of electrical generators for the OWC devises. The thesis initially aims to provide an accurate per-phase equivalent circuit model of the DFIM by investigating various characterisation testing procedures. Novel testing methodologies based on the series-coupling tests is employed and is found to provide a more accurate representation of the DFIM than the standard IEEE testing methods because the series-coupling tests provide a direct method of determining the equivalent-circuit resistances and inductances of the machine. A second novel method known as the extended short-circuit test is also presented and investigated as an alternative characterisation method. Experimental results on a 1.1 kW DFIM and a 30 kW DFIM utilising the various characterisation procedures are presented in the thesis. The various test methods are analysed and validated through comparison of model predictions and torque-versus-speed curves for each induction machine. Sensitivity analysis is also used as a means of quantifying the effect of experimental error on the results taken from each of the testing procedures and is used to determine the suitability of the test procedures for characterising each of the devices. The series-coupling differential test is demonstrated to be the optimum test. The research then focuses on the OWC WEC and the modelling of this device. A software model is implemented based on data obtained from a scaled prototype device situated at the Irish test site. Test data from the electrical system of the device is analysed and this data is used to develop a performance curve for the air turbine utilised in the WEC. This performance curve was applied in a software model to represent the turbine in the electro-mechanical system and the software results are validated by the measured electrical output data from the prototype test device. Finally, once both the DFIM and OWC WEC power take-off system have been modeled succesfully, an investigation of the application of the DFIM to the OWC WEC model is carried out to determine the electrical machine rating required for the pulsating power derived from OWC WEC device. Thermal analysis of a 30 kW induction machine is carried out using a first-order thermal model. The simulations quantify the limits of operation of the machine and enable thedevelopment of rating requirements for the electrical generation system of the OWC WEC. The thesis can be considered to have three sections. The first section of the thesis contains Chapters 2 and 3 and focuses on the accurate characterisation of the doubly-fed induction machine using various testing procedures. The second section, containing Chapter 4, concentrates on the modelling of the OWC WEC power-takeoff with particular focus on the Wells turbine. Validation of this model is carried out through comparision of simulations and experimental measurements. The third section of the thesis utilises the OWC WEC model from Chapter 4 with a 30 kW induction machine model to determine the optimum device rating for the specified machine. Simulations are carried out to perform thermal analysis of the machine to give a general insight into electrical machine rating for an OWC WEC device.

Engineering of metal oxide interfaces for renewable energy applications

Diminishing non-renewable energy resources and planet-wide de-pollution on our planet are among the major problems which mankind faces into the future. To solve these problems, renewable energy sources such as readily available and inexhaustible sunlight will have to be used. There are however no readily available photocatalysts that are photocatalytically active under visible light; it is well established that the band gap of the prototypical photocatalyst, titanium dioxide, is the UV region with the consequence that only 4% of sun light is utilized. For this reason, this PhD project focused on developing new materials, based on titanium dioxide, which can be used in visible light activated photocatalytic hydrogen production and destruction of pollutant molecules. The main goal of this project is to use simulations based on first principles to engineer and understand rationally, materials based on modifying TiO2 that will have the following properties: (1) a suitable band gap in order to increase the efficiency of visible light absorption, with a gap around 2 – 2.5 eV considered optimum. (2). The second key aspect in the photocatalytic process is electron and hole separation after photoexcitation, which enable oxidation/reduction reactions necessary to i.e. decompose pollutants. (3) Enhanced activity over unmodified TiO2. In this thesis I present results on new materials based on modifying TiO2 with supported metal oxide nanoclusters, from two classes, namely: transition metal oxides (Ti, Ni, Cu) and p-block metal oxides (Sn, Pb, Bi). We find that the deposited metal oxide nanoclusters are stable at rutile and anatase TiO2 surfaces and present an analysis of changes to the band gap of TiO2, identifying those modifiers that can change the band gap to the desirable range and the origin of this. A successful collaboration with experimental researchers in Japan confirms many of the simulation results where the origin of improved visible light photocatalytic activity of oxide nanocluster-modified TiO2 is now well understood. The work presented in this thesis, creates a road map for the design of materials with desired photocatalytic properties and contributes to better understanding these properties which are of great application in renewable energy utilization.

Energy harvesting system design and optimization for wireless sensor networks

Wireless sensor networks (WSN) are becoming widely adopted for many applications including complicated tasks like building energy management. However, one major concern for WSN technologies is the short lifetime and high maintenance cost due to the limited battery energy. One of the solutions is to scavenge ambient energy, which is then rectified to power the WSN. The objective of this thesis was to investigate the feasibility of an ultra-low energy consumption power management system suitable for harvesting sub-mW photovoltaic and thermoelectric energy to power WSNs. To achieve this goal, energy harvesting system architectures have been analyzed. Detailed analysis of energy storage units (ESU) have led to an innovative ESU solution for the target applications. Battery-less, long-lifetime ESU and its associated power management circuitry, including fast-charge circuit, self-start circuit, output voltage regulation circuit and hybrid ESU, using a combination of super-capacitor and thin film battery, were developed to achieve continuous operation of energy harvester. Low start-up voltage DC/DC converters have been developed for 1mW level thermoelectric energy harvesting. The novel method of altering thermoelectric generator (TEG) configuration in order to match impedance has been verified in this work. Novel maximum power point tracking (MPPT) circuits, exploring the fractional open circuit voltage method, were particularly developed to suit the sub-1mW photovoltaic energy harvesting applications. The MPPT energy model has been developed and verified against both SPICE simulation and implemented prototypes. Both indoor light and thermoelectric energy harvesting methods proposed in this thesis have been implemented into prototype devices. The improved indoor light energy harvester prototype demonstrates 81% MPPT conversion efficiency with 0.5mW input power. This important improvement makes light energy harvesting from small energy sources (i.e. credit card size solar panel in 500lux indoor lighting conditions) a feasible approach. The 50mm × 54mm thermoelectric energy harvester prototype generates 0.95mW when placed on a 60oC heat source with 28% conversion efficiency. Both prototypes can be used to continuously power WSN for building energy management applications in typical office building environment. In addition to the hardware development, a comprehensive system energy model has been developed. This system energy model not only can be used to predict the available and consumed energy based on real-world ambient conditions, but also can be employed to optimize the system design and configuration. This energy model has been verified by indoor photovoltaic energy harvesting system prototypes in long-term deployed experiments.

Integrated magnetic components for high-power high-current dc-dc converters

This thesis is focused on the design and development of an integrated magnetic (IM) structure for use in high-power high-current power converters employed in renewable energy applications. These applications require low-cost, high efficiency and high-power density magnetic components and the use of IM structures can help achieve this goal. A novel CCTT-core split-winding integrated magnetic (CCTT IM) is presented in this thesis. This IM is optimized for use in high-power dc-dc converters. The CCTT IM design is an evolution of the traditional EE-core integrated magnetic (EE IM). The CCTT IM structure uses a split-winding configuration allowing for the reduction of external leakage inductance, which is a problem for many traditional IM designs, such as the EE IM. Magnetic poles are incorporated to help shape and contain the leakage flux within the core window. These magnetic poles have the added benefit of minimizing the winding power loss due to the airgap fringing flux as they shape the fringing flux away from the split-windings. A CCTT IM reluctance model is developed which uses fringing equations to accurately predict the most probable regions of fringing flux around the pole and winding sections of the device. This helps in the development of a more accurate model as it predicts the dc and ac inductance of the component. A CCTT IM design algorithm is developed which relies heavily on the reluctance model of the CCTT IM. The design algorithm is implemented using the mathematical software tool Mathematica. This algorithm is modular in structure and allows for the quick and easy design and prototyping of the CCTT IM. The algorithm allows for the investigation of the CCTT IM boxed volume with the variation of input current ripple, for different power ranges, magnetic materials and frequencies. A high-power 72 kW CCTT IM prototype is designed and developed for use in an automotive fuelcell-based drivetrain. The CCTT IM design algorithm is initially used to design the component while 3D and 2D finite element analysis (FEA) software is used to optimize the design. Low-cost and low-power loss ferrite 3C92 is used for its construction, and when combined with a low number of turns results in a very efficient design. A paper analysis is undertaken which compares the performance of the high-power CCTT IM design with that of two discrete inductors used in a two-phase (2L) interleaved converter. The 2L option consists of two discrete inductors constructed from high dc-bias material. Both topologies are designed for the same worst-case phase current ripple conditions and this ensures a like-for-like comparison. The comparison indicates that the total magnetic component boxed volume of both converters is similar while the CCTT IM has significantly lower power loss. Experimental results for the 72 kW, (155 V dc, 465 A dc input, 420 V dc output) prototype validate the CCTT IM concept where the component is shown to be 99.7 % efficient. The high-power experimental testing was conducted at General Motors advanced technology center in Torrence, Los Angeles. Calorific testing was used to determine the power loss in the CCTT IM component. Experimental 3.8 kW results and a 3.8 kW prototype compare and contrast the ferrite CCTT IM and high dc-bias 2L concepts over the typical operating range of a fuelcell under like-for-like conditions. The CCTT IM is shown to perform better than the 2L option over the entire power range. An 8 kW ferrite CCTT IM prototype is developed for use in photovoltaic (PV) applications. The CCTT IM is used in a boost pre-regulator as part of the PV power stage. The CCTT IM is compared with an industry standard 2L converter consisting of two discrete ferrite toroidal inductors. The magnetic components are compared for the same worst-case phase current ripple and the experimental testing is conducted over the operation of a PV panel. The prototype CCTT IM allows for a 50 % reduction in total boxed volume and mass in comparison to the baseline 2L option, while showing increased efficiency.

Energy harvesting embedded wireless sensor system for building environment applications

For many wireless sensor networks applications, indoor light energy is the only ambient energy source commonly available. Many advantages and constraints co-exist in this technology. However, relatively few indoor light powered harvesters have been presented and much research remains to be carried out on a variety of related design considerations and trade-offs. This work presents a solution using the Tyndall mote and an indoor light powered wireless sensor node. It analyses design considerations on several issues such as indoor light characteristics, solar panel component choice, maximum power point tracking, energy storage elements and the trade-offs and choices between them.

Practical wireless sensor networks power consumption metrics for building energy management applications

The power consumption of wireless sensor networks (WSN) module is an important practical concern in building energy management (BEM) system deployments. A set of metrics are created to assess the power profiles of WSN in real world condition. The aim of this work is to understand and eventually eliminate the uncertainties in WSN power consumption during long term deployments and the compatibility with existing and emerging energy harvesting technologies. This paper investigates the key metrics in data processing, wireless data transmission, data sensing and duty cycle parameter to understand the system power profile from a practical deployment prospective. Based on the proposed analysis, the impacts of individual metric on power consumption in a typical BEM application are presented and the subsequent low power solutions are investigated.

Artificial opal photonic crystals and inverse opal structures - fundamentals and applications from optics to energy storage

Photonic crystals (PhCs) influence the propagation of light by their periodic variation in dielectric contrast or refractive index. This review outlines the attractive optical qualities inherent to most PhCs namely the presence of full or partial photonic band gaps and the possibilities they present towards the inhibition of spontaneous emission and the localization of light. Colloidal self-assembly of polymer or silica spheres is one of the most favoured and low cost methods for the formation of PhCs as artificial opals. The state of the art in growth methods currently used for colloidal self-assembly are discussed and the use of these structures for the formation of inverse opal architectures is then presented. Inverse opal structures with their porous and interconnected architecture span several technological arenas - optics and optoelectronics, energy storage, communications, sensor and biological applications. This review presents several of these applications and an accessible overview of the physics of photonic crystal optics that may be useful for opal and inverse opal researchers in general, with a particular emphasis on the recent use of these three-dimensional porous structures in electrochemical energy storage technology. Progress towards all-optical integrated circuits may lie with the concepts of the photonic crystal, but the unique optical and structural properties of these materials and the convergence of PhC and energy storage disciplines may facilitate further developments and non-destructive optical analysis capabilities for (electro)chemical processes that occur within a wide variety of materials in energy storage research.

Integrated CoPtP permanent magnets for MEMS electromagnetic energy harvesting applications

This work reports the development of integrated Co rich CoPtP hard magnetic material for MEMS applications such as Electromagnetic Vibration Energy Harvesting. We report a new method of electrodeposition compared to the conventional DC plating, involving a combination of forward and reverse pulses for optimized deposition of Co rich CoPtP hard magnetic material. This results in significant improvements in the microstructure of the developed films as the pulse reverse plated films are smooth, stress free and uniform. Such improvements in the structural properties are reflected in the hard magnetic properties of the material as well. The intrinsic coercivities of the pulse reverse deposited film are more than 6 times higher for both in-plane and out-of-plane measurement directions and the squareness of the hysteresis loops also improve due to the similar reasons.

Model and visualise the relationship between energy consumption and temperature distribution in cold rooms

In the area of food and pharmacy cold storage, temperature distribution is considered as a key factor. Inappropriate distribution of temperature during the cooling process in cold rooms will cause the deterioration of the quality of products and therefore shorten their life-span. In practice, in order to maintain the distribution of temperature at an appropriate level, large amount of electrical energy has to be consumed to cool down the volume of space, based on the reading of a single temperature sensor placed in every cold room. However, it is not clear and visible that what is the change of energy consumption and temperature distribution over time. It lacks of effective tools to visualise such a phenomenon. In this poster, we initially present a solution which combines a visualisation tool with a Computational Fluid Dynamics (CFD) model together to enable users to explore such phenomenon.

Applications of finite element computer modelling and thermal infrared remote sensing to the study of geothermal anomalies

Buried heat sources can be investigated by examining thermal infrared images and comparing these with the results of theoretical models which predict the thermal anomaly a given heat source may generate. Key factors influencing surface temperature include the geometry and temperature of the heat source, the surface meteorological environment, and the thermal conductivity and anisotropy of the rock. In general, a geothermal heat flux of greater than 2% of solar insolation is required to produce a detectable thermal anomaly in a thermal infrared image. A heat source of, for example, 2-300K greater than the average surface temperature must be a t depth shallower than 50m for the detection of the anomaly in a thermal infrared image, for typical terrestrial conditions. Atmospheric factors are of critical importance. While the mean atmospheric temperature has little significance, the convection is a dominant factor, and can act to swamp the thermal signature entirely. Given a steady state heat source that produces a detectable thermal anomaly, it is possible to loosely constrain the physical properties of the heat source and surrounding rock, using the surface thermal anomaly as a basis. The success of this technique is highly dependent on the degree to which the physical properties of the host rock are known. Important parameters include the surface thermal properties and thermal conductivity of the rock. Modelling of transient thermal situations was carried out, to assess the effect of time dependant thermal fluxes. One-dimensional finite element models can be readily and accurately applied to the investigation of diurnal heat flow, as with thermal inertia models. Diurnal thermal models of environments on Earth, the Moon and Mars were carried out using finite elements and found to be consistent with published measurements. The heat flow from an injection of hot lava into a near surface lava tube was considered. While this approach was useful for study, and long term monitoring in inhospitable areas, it was found to have little hazard warning utility, as the time taken for the thermal energy to propagate to the surface in dry rock (several months) in very long. The resolution of the thermal infrared imaging system is an important factor. Presently available satellite based systems such as Landsat (resolution of 120m) are inadequate for detailed study of geothermal anomalies. Airborne systems, such as TIMS (variable resolution of 3-6m) are much more useful for discriminating small buried heat sources. Planned improvements in the resolution of satellite based systems will broaden the potential for application of the techniques developed in this thesis. It is important to note, however, that adequate spatial resolution is a necessary but not sufficient condition for successful application of these techniques.

The development of a computer model to optimize the performance of a 50kWp photovoltaic system

A computer model has been developed to optimize the performance of a 50kWp photovoltaic system which supplies electrical energy to a dairy farm at Fota Island in Cork Harbour. Optimization of the system involves maximising the efficiency and increasing the performance and reliability of each hardware unit. The model accepts horizontal insolation, ambient temperature, wind speed, wind direction and load demand as inputs. An optimization program uses the computer model to simulate the optimum operating conditions. From this analysis, criteria are established which are used to improve the photovoltaic system operation. This thesis describes the model concepts, the model implementation and the model verification procedures used during development. It also describes the techniques which are used during system optimization. The software, which is written in FORTRAN, is structured in modular units to provide logical and efficient programming. These modular units may also be used in the modelling and optimization of other photovoltaic systems.

Energy storage systems for wave energy converters and microgrids

The thesis initially gives an overview of the wave industry and the current state of some of the leading technologies as well as the energy storage systems that are inherently part of the power take-off mechanism. The benefits of electrical energy storage systems for wave energy converters are then outlined as well as the key parameters required from them. The options for storage systems are investigated and the reasons for examining supercapacitors and lithium-ion batteries in more detail are shown. The thesis then focusses on a particular type of offshore wave energy converter in its analysis, the backward bent duct buoy employing a Wells turbine. Variable speed strategies from the research literature which make use of the energy stored in the turbine inertia are examined for this system, and based on this analysis an appropriate scheme is selected. A supercapacitor power smoothing approach is presented in conjunction with the variable speed strategy. As long component lifetime is a requirement for offshore wave energy converters, a computer-controlled test rig has been built to validate supercapacitor lifetimes to manufacturer’s specifications. The test rig is also utilised to determine the effect of temperature on supercapacitors, and determine application lifetime. Cycle testing is carried out on individual supercapacitors at room temperature, and also at rated temperature utilising a thermal chamber and equipment programmed through the general purpose interface bus by Matlab. Application testing is carried out using time-compressed scaled-power profiles from the model to allow a comparison of lifetime degradation. Further applications of supercapacitors in offshore wave energy converters are then explored. These include start-up of the non-self-starting Wells turbine, and low-voltage ride-through examined to the limits specified in the Irish grid code for wind turbines. These applications are investigated with a more complete model of the system that includes a detailed back-to-back converter coupling a permanent magnet synchronous generator to the grid. Supercapacitors have been utilised in combination with battery systems for many applications to aid with peak power requirements and have been shown to improve the performance of these energy storage systems. The design, implementation, and construction of coupling a 5 kW h lithium-ion battery to a microgrid are described. The high voltage battery employed a continuous power rating of 10 kW and was designed for the future EV market with a controller area network interface. This build gives a general insight to some of the engineering, planning, safety, and cost requirements of implementing a high power energy storage system near or on an offshore device for interface to a microgrid or grid.

Investigation of lactic acid bacteria mediated bioprotection with applications in cereal industry. Case-study: malting process

Antifungal compounds produced by Lactic acid bacteria (LAB) metabolites can be natural and reliable alternative for reducing fungal infections pre- and post-harvest with a multitude of additional advantages for cereal-base products. Toxigenic and spoilage fungi are responsible for numerous diseases and economic losses. This thesis includes an overview of the impact fungi have on aspects of the cereal food chain. The applicability of LAB in plant protection and cereal industry is discussed in detail. Specific case studies include Fusarium head blight, and the impact of fungi in the malting and baking industry. The impact of Fusarium culmorum infected raw barley on the final malt quality was part of the investigation. In vitro infected barley grains were fully characterized. The study showed that the germinative energy of infected barley grains decreased by 45% and grains accumulated 199 μg.kg-1 of deoxynivalenol (DON). Barley grains were subsequently malted and fully characterized. Fungal biomass increased during all stages of malting. Infected malt accumulated 8-times its DON concentration during malting. Infected malt grains revealed extreme structural changes due to proteolytic, (hemi)-cellulolytic and starch degrading activity of the fungi, this led to increased friability and fragmentation. Infected grains also had higher protease and β-glucanase activities, lower amylase activity, a greater proportion of free amino and soluble nitrogen, and a lower β-glucan content. Malt loss was over 27% higher in infected malt when compared to the control. The protein compositional changes and respective enzymatic activity of infected barley and respective malt were characterized using a wide range of methods. F. culmorum infected barley grains showed an increase in proteolytic activity and protein extractability. Several metabolic proteins decreased and increased at different rates during infection and malting, showing a complex F. culmorum infection interdependence. In vitro F. culmorum infected malt was used to produce lager beer to investigate changes caused by the fungi during the brewing processes and their effect on beer quality attributes. It was found, that the wort containing infected malt had a lower pH, a higher FAN, higher β-glucan and a 45% increase in the purging rate, and led to premature yeast flocculation. The beer produced with infected malt (IB) had also a significantly different amino acid profile. IB flavour characterization revealed a higher concentration of esters, fusel alcohols, fatty acids, ketones, and dimethylsulfide, and in particular, acetaldehyde, when compared to the control. IB had a greater proportion of Strecker aldehydes and Maillard products contributing to an increased beer staling character. IB resulted in a 67% darker colour with a trend to better foam stability. It was also found that 78% of the accumulated mycotoxin deoxynivalenol in the malt was transferred into beer. A LAB cell-freesupernatant (cfs), produced in wort-base substrate, was investigated for its ability to inhibit Fusarium growth during malting. Wort was a suitable substrate for LAB exhibiting antifungal activity. Lactobacillus amylovorus DSM19280 inhibited 104 spores.mL-1 for 7 days, after 120 h of fermentation, while Lactobacillus reuteri R29 inhibited 105 spores.mL-1 for 7 days, after 48 h of fermentation. Both LAB cfs had significant different organic acid profiles. Acid-base antifungal compounds were identified and, phenyllactic, hydroxy-phenyllactic, and benzoic acids were present in higher concentrations when compared to the control. A 3 °P wort substrate inoculated With L. reuteri R29 (cfs) was applied in malting and successfully inhibited Fusarium growth by 23%, and mycotoxin DON by 80%. Malt attributes resulted in highly modified grains, lower pH, higher colouration, and higher extract yield. The implementation of selected LAB producing antifungal compounds can be used successfully in the malting process to reduce mould growth and mycotoxin production.

First principles simulation of amorphous silicon bulk, interfaces, and nanowires for photovoltaics

Amorphous silicon has become the material of choice for many technologies, with major applications in large area electronics: displays, image sensing and thin film photovoltaic cells. This technology development has occurred because amorphous silicon is a thin film semiconductor that can be deposited on large, low cost substrates using low temperature. In this thesis, classical molecular dynamics and first principles DFT calculations have been performed to generate structural models of amorphous and hydrogenated amorphous silicon and interfaces of amorphous and crystalline silicon, with the ultimate aim of understanding the photovoltaic properties of core-shell crystalline amorphous Si nanowire structures. We have shown, unexpectedly, from the simulations, that our understanding of hydrogenated bulk a-Si needs to be revisited, with our robust finding that when fully saturated with hydrogen, bulk a-Si exhibits a constant optical energy gap, irrespective of the hydrogen concentration in the sample. Unsaturated a-Si:H, with a lower than optimum hydrogen content, shows a smaller optical gap, that increases with hydrogen content until saturation is reached. The mobility gaps obtained from an analysis of the electronic states show similar behavior. We also obtained that the optical and mobility gaps show a volcano curve as the H content is varied from 7% (undersaturation) to 18% (mild oversaturation). In the case of mild over saturation, the mid-gap states arise exclusively from an increase in the density of strained Si-Si bonds. Analysis of our structures shows the extra H atoms in this case form a bridge between neighboring silicon atoms which increases the corresponding Si-Si distance and promotes bond length disorder in the sample. That has the potential to enhance the Staebler-Wronski effect. Planar interface models of amorphous-crystalline silicon have been generated in Si (100), (110) and (111) surfaces. The interface models are characterized by structure, RDF, electronic density of states and optical absorption spectrum. We find that the least stable (100) surface will result in the formation of the thickest amorphous silicon layer, while the most stable (110) surface forms the smallest amorphous region. We calculated for the first time band offsets of a-Si:H/c-Si heterojunctions from first principles and examined the influence of different surface orientations and amorphous layer thickness on the offsets and implications for device performance. The band offsets depend on the amorphous layer thickness and increase with thickness. By controlling the amorphous layer thickness we can potentially optimise the solar cell parameters. Finally, we have successfully generated different amorphous layer thickness of the a-Si/c-Si and a-Si:H/c-Si 5 nm nanowires from heat and quench. We perform structural analysis of the a-Si-/c-Si nanowires. The RDF, Si-Si bond length distributions, and the coordination number distributions of amorphous regions of the nanowires reproduce similar behaviour compared to bulk amorphous silicon. In the final part of this thesis we examine different surface terminating chemical groups, -H, - OH and –NH2 in (001) GeNW. Our work shows that the diameter of Ge nanowires and the nature of surface terminating groups both play a significant role in both the magnitude and the nature of the nanowire band gaps, allowing tuning of the band gap by up to 1.1 eV. We also show for the first time how the nanowire diameter and surface termination shifts the absorption edge in the Ge nanowires to longer wavelengths. Thus, the combination of nanowire diameter and surface chemistry can be effectively utilised to tune the band gaps and thus light absorption properties of small diameter Ge nanowires.

Theory of the electronic and optical properties of dilute bismide alloys

Dilute bismide alloys, containing small fractions of bismuth (Bi), have recently attracted interest due to their potential for applications in a range of semiconductor devices. Experiments have revealed that dilute bismide alloys such as GaBixAs1−x, in which a small fraction x of the atoms in the III-V semiconductor GaAs are replaced by Bi, exhibit a number of unusual and unique properties. For example, the band gap energy (E g) decreases rapidly with increasing Bi composition x, by up to 90 meV per % Bi replacing As in the alloy. This band gap reduction is accompanied by a strong increase in the spin-orbit-splitting energy (ΔSO) with increasing x, and both E g and ΔSO are characterised by strong, composition-dependent bowing. The existence of a ΔSO > E g regime in the GaBixAs1−x alloy has been demonstrated for x ≳10%, a band structure condition which is promising for the development of highly efficient, temperature stable semiconductor lasers that could lead to large energy savings in future optical communication networks. In addition to their potential for specific applications, dilute bismide alloys have also attracted interest from a fundamental perspective due to their unique properties. In this thesis we develop the theory of the electronic and optical properties of dilute bismide alloys. By adopting a multi-scale approach encompassing atomistic calculations of the electronic structure using the semi-empirical tight-binding method, as well as continuum calculations based on the k•p method, we develop a fundamental understanding of this unusual class of semiconductor alloys and identify general material properties which are promising for applications in semiconductor optoelectronic and photovoltaic devices. By performing detailed supercell calculations on both ordered and disordered alloys we explicitly demonstrate that Bi atoms act as isovalent impurities when incorporated in dilute quantities in III-V (In)GaAs(P) materials, strongly perturbing the electronic structure of the valence band. We identify and quantify the causes and consequences of the unusual electronic properties of GaBixAs1−x and related alloys, and our analysis is reinforced throughout by a series of detailed comparisons to the results of experimental measurements. Our k•p models of the band structure of GaBixAs1−x and related alloys, which we derive directly from detailed atomistic calculations, are ideally suited to the study of dilute bismide-based devices. We focus in the latter part of the thesis on calculations of the electronic and optical properties of dilute bismide quantum well lasers. In addition to developing an understanding of the effects of Bi incorporation on the operational characteristics of semiconductor lasers, we also present calculations which have been used explicitly in designing and optimising the first generation of GaBixAs1−x-based devices.