Optical emission of strained direct-band-gap Ge quantum well embedded inside InGaAs alloy layers

We studied the optical properties of a strain-induced direct-band-gap Ge quantum well embedded in InGaAs. We showed that the band offsets depend on the electronegativity of the layer in contact with Ge, leading to different types of optical transitions in the heterostructure. When group-V atoms compose the interfaces, only electrons are confined in Ge, whereas both carriers are confined when the interface consists of group-III atoms. The different carrier confinement results in different emission dynamics behavior. This study provides a solution to obtain efficient light emission from Ge.

Modifying the band gap and optical properties of Germanium nanowires by surface termination

Semiconductor nanowires, based on silicon (Si) or germanium (Ge) are leading candidates for many ICT applications, including next generation transistors, optoelectronics, gas and biosensing and photovoltaics. Key to these applications is the possibility to tune the band gap by changing the diameter of the nanowire. Ge nanowires of different diameter have been studied with H termination, but, using ideas from chemistry, changing the surface terminating group can be used to modulate the band gap. In this paper we apply the generalised gradient approximation of density functional theory (GGA-DFT) and hybrid DFT to study the effect of diameter and surface termination using –H, –NH2 and –OH groups on the band gap of (001), (110) and (111) oriented germanium nanowires. We show that the surface terminating group allows both the magnitude and the nature of the band gap to be changed. We further show that the absorption edge shifts to longer wavelength with the –NH2 and –OH terminations compared to the –H termination and we trace the origin of this effect to valence band modifications upon modifying the nanowire with –NH2 or –OH. These results show that it is possible to tune the band gap of small diameter Ge nanowires over a range of ca. 1.1 eV by simple surface chemistry.

Investigating routes toward atomic layer deposition of silicon carbide: Ab initio screening of potential silicon and carbon precursors

Silicon carbide (SiC) is a promising material for electronics due to its hardness, and ability to carry high currents and high operating temperature. SiC films are currently deposited using chemical vapor deposition (CVD) at high temperatures 1500–1600 °C. However, there is a need to deposit SiC-based films on the surface of high aspect ratio features at low temperatures. One of the most precise thin film deposition techniques on high-aspect-ratio surfaces that operates at low temperatures is atomic layer deposition (ALD). However, there are currently no known methods for ALD of SiC. Herein, the authors present a first-principles thermodynamic analysis so as to screen different precursor combinations for SiC thin films. The authors do this by calculating the Gibbs energy ΔGΔG of the reaction using density functional theory and including the effects of pressure and temperature. This theoretical model was validated for existing chemical reactions in CVD of SiC at 1000 °C. The precursors disilane (Si2H6), silane (SiH4), or monochlorosilane (SiH3Cl) with ethyne (C2H2), carbontetrachloride (CCl4), or trichloromethane (CHCl3) were predicted to be the most promising for ALD of SiC at 400 °C.

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.

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.

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.

Surfactant-mediated variation of band-edge emission in CdS nanocomposites

The optical-structural characteristics of the direct optical band-gap semiconducting series of surfactant template-mediated laminar (CdS)x(CdCl2)y(CnH2n+4N)z nanocomposites are reported. X-ray diffraction measurements of the nanocomposites exhibited interlaminar distances in the range 2.9-3.6 nm with observations of eighth order {0 0 l} diffraction planes indicative of a high degree of laminarity and crystallographic order. Diffuse reflectance measurements have determined that the profile of their emission spectrum is that of a direct band-gap with absorption edges in the range 2.11-2.40 eV, depending on the CdS mole fraction in the nanocomposite. Photoluminescence (PL) excitation and time-resolved PL spectroscopies give an estimate of the maximum relative absorbance of the nanocomposites at ∼420 nm while the minimum was observed at ∼560 nm. The main emission was observed at ∼700 nm with emission from doubly ionized sulphur vacancies observed at ∼615 nm at room temperature. The CdS-containing nanocomposite is thus a surfactant-mediated modular system with variable band-gap energy emission.

Experimental impulse radio IEEE 802.15.4a UWB based wireless sensor localization technology: Characterization, reliability and ranging

Ultra Wide Band (UWB) transmission has recently been the object of considerable attention in the field of next generation location aware wireless sensor networks. This is due to its fine time resolution, energy efficient and robustness to interference in harsh environments. This paper presents a thorough applied examination of prototype IEEE 802.15.4a impulse UWB transceiver technology to quantify the effect of line of sight (LOS) and non line of sight (NLOS) ranging in real indoor and outdoor environments. Results included draw on an extensive array of experiments that fully characterize the 802.15.4a UWB transceiver technology, its reliability and ranging capabilities for the first time. A new two way (TW) ranging protocol is proposed. The goal of this work is to validate the technology as a dependable wireless communications mechanism for the subset of sensor network localization applications where reliability and precision positions are key concerns.

Properties of molecules in tunnel junctions

Molecular tunnel junctions involve studying the behaviour of a single molecule sandwiched between metal leads. When a molecule makes contact with electrodes, it becomes open to the environment which can heavily influence its properties, such as electronegativity and electron transport. While the most common computational approaches remain to be single particle approximations, in this thesis it is shown that a more explicit treatment of electron interactions can be required. By studying an open atomic chain junction, it is found that including electron correlations corrects the strong lead-molecule interaction seen by the ΔSCF approximation, and has an impact on junction I − V properties. The need for an accurate description of electronegativity is highlighted by studying a correlated model of hexatriene-di-thiol with a systematically varied correlation parameter and comparing the results to various electronic structure treatments. The results indicating an overestimation of the band gap and underestimation of charge transfer in the Hartree-Fock regime is equivalent to not treating electron-electron correlations. While in the opposite limit, over-compensating for electron-electron interaction leads to underestimated band gap and too high an electron current as seen in DFT/LDA treatment. It is emphasised in this thesis that correcting electronegativity is equivalent to maximising the overlap of the approximate density matrix to the exact reduced density matrix found at the exact many-body solution. In this work, the complex absorbing potential (CAP) formalism which allows for the inclusion metal electrodes into explicit wavefunction many-body formalisms is further developed. The CAP methodology is applied to study the electron state lifetimes and shifts as the junction is made open.

Carbon nanotubes as materials in nanotechnology

Carbon nanotubes (CNTs) are hollow tubes of sp2-hybridised carbon with diameters of the order of nanometres. Due to their unique physical properties, which include ballistic transport and high mechanical strength, they are of significant interest for technological applications. The electronic properties of CNTs are of particular interest for use as gas sensors, interconnect materials in the semi-conductor industry and as the channel material in CNT based field effect transistors. The primary difficulty associated with the use of CNTs in electronic applications is the inability to control electronic properties at the growth stage; as grown CNTs consist of a mixture of metallic and semi-conducting CNTs. Doping has the potential to solve this problem and is a focus of this thesis. Nitrogen-doped CNTs typically have defective structures; the usual hollow CNT structure is replaced by a series of compartments. Through density functional theory (DFT) calculations and experimental results, we propose an explanation for the defective structures obtained, based on the stronger binding of N to the growth catalyst in comparison to C. In real electronic devices, CNTs need to be contacted to metal, we generate the current-voltage (IV) characteristics of metal-contacted CNTs considering both the effect of dopants and the structure of the interface region on electronic properties. We find that substitutionally doped CNTs produce Ohmic contacts and that scattering at the interface is strongly influenced by structure. In addition, we consider the effect of the common vacancy defects on the electronic properties of large diameter CNTs. Defects increase scattering in the CNT, with the greatest scattering occurring for the largest defect (555777). We validate the independent scattering approximation for small diameter CNTs, which enables mean free paths in large diameter CNTs to be calculated, with a smaller mean free paths found for larger defects.

Ab initio calculations of group 4 metallocene reaction mechanisms: atomic layer deposition and bond activation catalysis

Thin film dielectrics based on titanium, zirconium or hafnium oxides are being introduced to increase the permittivity of insulating layers in transistors for micro/nanoelectronics and memory devices. Atomic layer deposition (ALD) is the process of choice for fabricating these films, as it allows for high control of composition and thickness in thin, conformal films which can be deposited on substrates with high aspect-ratio features. The success of this method depends crucially on the chemical properties of the precursor molecules. A successful ALD precursor should be volatile, stable in the gas-phase, but reactive on the substrate and growing surface, leading to inert by-products. In recent years, many different ALD precursors for metal oxides have been developed, but many of them suffer from low thermal stability. Much promise is shown by group 4 metal precursors that contain cyclopentadienyl (Cp = C5H5-xRx) ligands. One of the main advantages of Cp precursors is their thermal stability. In this work ab initio calculations were carried out at the level of density functional theory (DFT) on a range of heteroleptic metallocenes [M(Cp)4-n(L)n], M = Hf/Zr/Ti, L = Me and OMe, in order to find mechanistic reasons for their observed behaviour during ALD. Based on optimized monomer structures, reactivity is analyzed with respect to ligand elimination. The order in which different ligands are eliminated during ALD follows their energetics which was in agreement with experimental measurements. Titanocene-derived precursors, TiCp*(OMe)3, do not yield TiO2 films in atomic layer deposition (ALD) with water, while Ti(OMe)4 does. DFT was used to model the ALD reaction sequence and find the reason for the difference in growth behaviour. Both precursors adsorb initially via hydrogen-bonding. The simulations reveal that the Cp* ligand of TiCp*(OMe)3 lowers the Lewis acidity of the Ti centre and prevents its coordination to surface O (densification) during both of the ALD pulses. Blocking this step hindered further ALD reactions and for that reason no ALD growth is observed from TiCp*(OMe)3 and water. The thermal stability in the gas phase of Ti, Zr and Hf precursors that contain cyclopentadienyl ligands was also considered. The reaction that was found using DFT is an intramolecular α-H transfer that produces an alkylidene complex. The analysis shows that thermal stabilities of complexes of the type MCp2(CH3)2 increase down group 4 (M = Ti, Zr and Hf) due to an increase in the HOMO-LUMO band gap of the reactants, which itself increases with the electrophilicity of the metal. The reverse reaction of α-hydrogen abstraction in ZrCp2Me2 is 1,2-addition reaction of a C-H bond to a Zr=C bond. The same mechanism is investigated to determine if it operates for 1,2 addition of the tBu C-H across Hf=N in a corresponding Hf dimer complex. The aim of this work is to understand orbital interactions, how bonds break and how new bonds form, and in what state hydrogen is transferred during the reaction. Calculations reveal two synchronous and concerted electron transfers within a four-membered cyclic transition state in the plane between the cyclopentadienyl rings, one π(M=X)-to-σ(M-C) involving metal d orbitals and the other σ(C-H)-to-σ(X-H) mediating the transfer of neutral H, where X = C or N. The reaction of the hafnium dimer complex with CO that was studied for the purpose of understanding C-H bond activation has another interesting application, namely the cleavage of an N-N bond and resulting N-C bond formation. Analysis of the orbital plots reveals repulsion between the occupied orbitals on CO and the N-N unit where CO approaches along the N-N axis. The repulsions along the N-N axis are minimized by instead forming an asymmetrical intermediate in which CO first coordinates to one Hf and then to N. This breaks the symmetry of the N-N unit and the resultant mixing of MOs allows σ(NN) to be polarized, localizing electrons on the more distant N. This allowed σ(CO) and π(CO) donation to N and back-donation of π*(Hf2N2) to CO. Improved understanding of the chemistry of metal complexes can be gained from atomic-scale modelling and this provides valuable information for the design of new ALD precursors. The information gained from the model decomposition pathway can be additionally used to understand the chemistry of molecules in the ALD process as well as in catalytic systems.

Reactivity of sub 1 nm supported clusters: (TiO2)(n) clusters supported on rutile TiO2 (110)

Metal oxide clusters of sub-nm dimensions dispersed on a metal oxide support are an important class of catalytic materials for a number of key chemical reactions, showing enhanced reactivity over the corresponding bulk oxide. In this paper we present the results of a density functional theory study of small sub-nm TiO2 clusters, Ti2O4, Ti3O6 and Ti4O8 supported on the rutile (110) surface. We find that all three clusters adsorb strongly with adsorption energies ranging from -3 eV to -4.5 eV. The more stable adsorption structures show a larger number of new Ti-O bonds formed between the cluster and the surface. These new bonds increase the coordination of cluster Ti and O as well as surface oxygen, so that each has more neighbours. The electronic structure shows that the top of the valence band is made up of cluster derived states, while the conduction band is made up of Ti 3d states from the surface, resulting in a reduction of the effective band gap and spatial separation of electrons and holes after photon absorption, which shows their potential utility in photocatalysis. To examine reactivity, we study the formation of oxygen vacancies in the cluster-support system. The most stable oxygen vacancy sites on the cluster show formation energies that are significantly lower than in bulk TiO2, demonstrating the usefulness of this composite system for redox catalysis.

High speed optical communication systems: From modulation formats to radically new fibres

High volumes of data traffic along with bandwidth hungry applications, such as cloud computing and video on demand, is driving the core optical communication links closer and closer to their maximum capacity. The research community has clearly identifying the coming approach of the nonlinear Shannon limit for standard single mode fibre [1,2]. It is in this context that the work on modulation formats, contained in Chapter 3 of this thesis, was undertaken. The work investigates the proposed energy-efficient four-dimensional modulation formats. The work begins by studying a new visualisation technique for four dimensional modulation formats, akin to constellation diagrams. The work then carries out one of the first implementations of one such modulation format, polarisation-switched quadrature phase-shift keying (PS-QPSK). This thesis also studies two potential next-generation fibres, few-mode and hollow-core photonic band-gap fibre. Chapter 4 studies ways to experimentally quantify the nonlinearities in few-mode fibre and assess the potential benefits and limitations of such fibres. It carries out detailed experiments to measure the effects of stimulated Brillouin scattering, self-phase modulation and four-wave mixing and compares the results to numerical models, along with capacity limit calculations. Chapter 5 investigates hollow-core photonic band-gap fibre, where such fibres are predicted to have a low-loss minima at a wavelength of 2μm. To benefit from this potential low loss window requires the development of telecoms grade subsystems and components. The chapter will outline some of the development and characterisation of these components. The world's first wavelength division multiplexed (WDM) subsystem directly implemented at 2μm is presented along with WDM transmission over hollow-core photonic band-gap fibre at 2μm. References: [1]P. P. Mitra, J. B. Stark, Nature, 411, 1027-1030, 2001 [2] A. D. Ellis et al., JLT, 28, 423-433, 2010.

Two closely coupled lasers, dynamics & applications

The dynamics of two mutually coupled identical single-mode semi-conductor lasers are theoretically investigated. For small separation and large coupling between the lasers, symmetry-broken one-colour states are shown to be stable. In this case the light output of the lasers have significantly different intensities whilst at the same time the lasers are locked to a single common frequency. For intermediate coupling we observe stable two-colour states, where both single-mode lasers lase simultaneously at two optical frequencies which are separated by up to 150 GHz. For low coupling but possibly large separation, the frequency of the relaxation oscillations of the freerunning lasers defines the dynamics. Chaotic and quasi-periodic states are identified and shown to be stable. For weak coupling undamped relaxation oscillations dominate where each laser is locked to three or more odd number of colours spaced by the relaxation oscillation frequency. It is shown that the instabilities that lead to these states are directly connected to the two colour mechanism where the change in the number of optical colours due to a change in the plane of oscillation. At initial coupling, in-phase and anti-phase one colour states are shown to emerge from “on” uncoupled lasers using a perturbation method. Similarly symmetry-broken one-colour states come from considering one free-running laser initially “on” and the other laser initially “off”. The mechanism that leads to a bi-stability between in-phase and anti-phase one-colour states is understood. Due to an equivariant phase space symmetry of being able to exchange the identical lasers, a symmetric and symmetry-broken variant of all states mentioned above exists and is shown to be stable. Using a five dimensional model we identify the bifurcation structure which is responsible for the appearance of symmetric and symmetry-broken one-colour, symmetric and symmetry-broken two-colour, symmetric and symmetry-broken undamped relaxation oscillations, symmetric and symmetry-broken quasi-periodic, and symmetric and symmetry-broken chaotic states. As symmetry-broken states always exist in pairs, they naturally give rise to bi-stability. Several of these states show multistabilities between symmetric and symmetry-broken variants and among states. Three memory elements on the basis of bi-stabilities in one and two colour states for two coupled single-mode lasers are proposed. The switching performance of selected designs of optical memory elements is studied numerically.

Polymer and metallodielectric based photonic crystals

The bottom-up colloidal synthesis of photonic crystals has attracted interest over top-down approaches due to their relatively simplicity, the potential to produce large areas, and the low-costs with this approach in fabricating complex 3-dimensional structures. This thesis focuses on the bottom-up approach in the fabrication of polymeric colloidal photonic crystals and their subsequent modification. Poly(methyl methacrylate) sub-micron spheres were used to produce opals, inverse opals and 3D metallodielectric photonic crystal (MDPC) structures. The fabrication of MDPCs with Au nanoparticles attached to the PMMA spheres core–shell particles is described. Various alternative procedures for the fabrication of photonic crystals and MDPCs are described and preliminary results on the use of an Au-based MDPC for surface-enhanced Raman scattering (SERS) are presented. These preliminary results suggest a threefold increase of the Raman signal with the MDPC as compared to PMMA photonic crystals. The fabrication of PMMA-gold and PMMA-nickel MDPC structures via an optimised electrodeposition process is described. This process results in the formation of a continuous dielectric-metal interface throughout a 3D inverted photonic crystal structure, which are shown to possess interesting optical properties. The fabrication of a robust 3D silica inverted structure with embedded Au nanoparticles is described by a novel co-crystallisation method which is capable of creating a SiO2/Au NP composite structure in a single step process. Although this work focuses on the creation of photonic crystals, this co-crystallisation approach has potential for the creation of other functional materials. A method for the fabrication of inverted opals containing silicon nanoparticles using aerosol assisted chemical vapour deposition is described. Silicon is a high dielectric material and nanoparticles of silicon can improve the band gap and absorption properties of the resulting structure, and therefore have the potential to be exploited in photovoltaics.