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.

Controlling alloy formation and optical properties by galvanic replacement of sub-20 nm silver nanoparticles in organic media

Galvanic replacement is a versatile synthetic strategy for the synthesis of alloy and hollow nanostructures. The structural evolution of single crystalline and multiply twinned nanoparticles <20 nm in diameter and capped with oleylamine is systematically studied. Changes in chemical composition are dependent on the size and crystallinity of the parent nanoparticle. The effects of reaction temperature and rate of precursor addition are also investigated. Galvanic replacement of single crystal spherical and truncated cubic nanoparticles follows the same mechanism to form hollow octahedral nanoparticles, a mechanism which is not observed for galvanic replacement of Ag templates in aqueous systems. Multiply twinned nanoparticles can form nanorings or solid alloys by manipulating the reaction conditions. Oleylamine-capped Ag nanoparticles are highly adaptable templates to synthesize a range of hollow and alloy nanostructures with tuneable localised surface plasmon resonance.

Plasmonic gold nanostructures: optical properties and application in mercury detection

This thesis investigates the application of plasmonic gold nanostructures for mercury detection. Various gold and silver single nanostructures and gold nanostructure assemblies were characterised in detail by correlated single nanostructure spectroscopy and electron microscopy. Several routes for mercury detection were explored: plasmon resonance energy transfer (PRET) upon Hg2+ binding to immobilised gold nanoparticle-organic ligand hybrid structures and amalgamation of single immobilised gold nanorods upon chemical and upon electrochemical reduction of Hg2+ ions. The amalgamation approach showed large potential with extraordinary shifts of the nanorods’ scattering spectra upon exposure to reduced mercury; a result of compositional and morphological change induced in the nanorod by amalgamation with mercury. A shift of 5 nm could be recorded for a concentration as low 10 nM Hg2+. Through detailed time-dependent experiments insights into the amalgamation mechanism were gained and a model comprising 5 steps was developed. Finally, spectroelectrochemistry proved to be an excellent way to study in real time in-situ the amalgamation of mercury with gold nanorods paving the way for future work in this field.

Evaluating the spatial transferability and temporal repeatability of remote-sensing-based lake water quality retrieval algorithms at the European scale: a meta-analysis approach

Many studies have shown the considerable potential for the application of remote-sensing-based methods for deriving estimates of lake water quality. However, the reliable application of these methods across time and space is complicated by the diversity of lake types, sensor configuration, and the multitude of different algorithms proposed. This study tested one operational and 46 empirical algorithms sourced from the peer-reviewed literature that have individually shown potential for estimating lake water quality properties in the form of chlorophyll-a (algal biomass) and Secchi disc depth (SDD) (water transparency) in independent studies. Nearly half (19) of the algorithms were unsuitable for use with the remote-sensing data available for this study. The remaining 28 were assessed using the Terra/Aqua satellite archive to identify the best performing algorithms in terms of accuracy and transferability within the period 2001–2004 in four test lakes, namely Vänern, Vättern, Geneva, and Balaton. These lakes represent the broad continuum of large European lake types, varying in terms of eco-region (latitude/longitude and altitude), morphology, mixing regime, and trophic status. All algorithms were tested for each lake separately and combined to assess the degree of their applicability in ecologically different sites. None of the algorithms assessed in this study exhibited promise when all four lakes were combined into a single data set and most algorithms performed poorly even for specific lake types. A chlorophyll-a retrieval algorithm originally developed for eutrophic lakes showed the most promising results (R2 = 0.59) in oligotrophic lakes. Two SDD retrieval algorithms, one originally developed for turbid lakes and the other for lakes with various characteristics, exhibited promising results in relatively less turbid lakes (R2 = 0.62 and 0.76, respectively). The results presented here highlight the complexity associated with remotely sensed lake water quality estimates and the high degree of uncertainty due to various limitations, including the lake water optical properties and the choice of methods.

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.

Aerosol properties associated with air masses arriving into the North East Atlantic during the 2008 Mace Head EUCAARI intensive observing period: an overview

As part of the EUCAARI Intensive Observing Period, a 4-week campaign to measure aerosol physical, chemical and optical properties, atmospheric structure, and cloud microphysics was conducted from mid-May to mid-June, 2008 at the Mace Head Atmospheric Research Station, located at the interface of Western Europe and the N. E. Atlantic and centered on the west Irish coastline. During the campaign, continental air masses comprising both young and aged continental plumes were encountered, along with polar, Arctic and tropical air masses. Polluted-continental aerosol concentrations were of the order of 3000 cm(-3), while background marine air aerosol concentrations were between 400-600 cm(-3). The highest marine air concentrations occurred in polar air masses in which a 15 nm nucleation mode, with concentration of 1100 cm(-3), was observed and attributed to open ocean particle formation. Continental air submicron chemical composition (excluding refractory sea salt) was dominated by organic matter, closely followed by sulphate mass. Although the concentrations and size distribution spectral shape were almost identical for the young and aged continental cases, hygroscopic growth factors (GF) and cloud condensation nuclei (CCN) to total condensation nuclei (CN) concentration ratios were significantly less in the younger pollution plume, indicating a more oxidized organic component to the aged continental plume. The difference in chemical composition and hygroscopic growth factor appear to result in a 40-50% impact on aerosol scattering coefficients and Aerosol Optical Depth, despite almost identical aerosol microphysical properties in both cases, with the higher values been recorded for the more aged case. For the CCN/CN ratio, the highest ratios were seen in the more age plume. In marine air, sulphate mass dominated the sub-micron component, followed by water soluble organic carbon, which, in turn, was dominated by methanesulphonic acid (MSA). Sulphate concentrations were highest in marine tropical air - even higher than in continental air. MSA was present at twice the concentrations of previously-reported concentrations at the same location and the same season. Both continental and marine air exhibited aerosol GFs significantly less than ammonium sulphate aerosol pointing to a significant organic contribution to all air mass aerosol properties.