Accommodating curvature in a highly ordered functionalized metal oxide nanofiber: synthesis, characterization and multi-scale modeling of layered nanosheets

A key element in the rational design of hybrid organic-inorganic nanostructures, is control of surfactant packing and adsorption onto the inorganic phase in crystal growth and assembly. In layered single crystal nanofibers and bilayered 2D nanosheets of vanadium oxide, we show how the chemisorption of preferred densities of surfactant molecules can direct formation of ordered, curved layers. The atom-scale features of the structures are described using molecular dynamics simulations that quantify surfactant packing effects and confirm the preference for a density of 5 dodecanethiol molecules per 8 vanadium attachment sites in the synthesised structures. This assembly maintains a remarkably well ordered interlayer spacing, even when curved. The assemblies of interdigitated organic bilayers on V2O5 are shown to be sufficiently flexible to tolerate curvature while maintaining a constant interlayer distance without rupture, delamination or cleavage. The accommodation of curvature and invariant structural integrity points to a beneficial role for oxide-directed organic film packing effects in layered architectures such as stacked nanofibers and hybrid 2D nanosheet systems.

Multi-scale modelling of atomic layer deposition

High-permittivity ("high-k") dielectric materials are used in the transistor gate stack in integrated circuits. As the thickness of silicon oxide dielectric reduces below 2 nm with continued downscaling, the leakage current because of tunnelling increases, leading to high power consumption and reduced device reliability. Hence, research concentrates on finding materials with high dielectric constant that can be easily integrated into a manufacturing process and show the desired properties as a thin film. Atomic layer deposition (ALD) is used practically to deposit high-k materials like HfO2, ZrO2, and Al2O3 as gate oxides. ALD is a technique for producing conformal layers of material with nanometer-scale thickness, used commercially in non-planar electronics and increasingly in other areas of science and technology. ALD is a type of chemical vapor deposition that depends on self-limiting surface chemistry. In ALD, gaseous precursors are allowed individually into the reactor chamber in alternating pulses. Between each pulse, inert gas is admitted to prevent gas phase reactions. This thesis provides a profound understanding of the ALD of oxides such as HfO2, showing how the chemistry affects the properties of the deposited film. Using multi-scale modelling of ALD, the kinetics of reactions at the growing surface is connected to experimental data. In this thesis, we use density functional theory (DFT) method to simulate more realistic models for the growth of HfO2 from Hf(N(CH3)2)4/H2O and HfCl4/H2O and for Al2O3 from Al(CH3)3/H2O.Three major breakthroughs are discovered. First, a new reaction pathway, ’multiple proton diffusion’, is proposed for the growth of HfO2 from Hf(N(CH3)2)4/H2O.1 As a second major breakthrough, a ’cooperative’ action between adsorbed precursors is shown to play an important role in ALD. By this we mean that previously-inert fragments can become reactive once sufficient molecules adsorb in their neighbourhood during either precursor pulse. As a third breakthrough, the ALD of HfO2 from Hf(N(CH3)2)4 and H2O is implemented for the first time into 3D on-lattice kinetic Monte-Carlo (KMC).2 In this integrated approach (DFT+KMC), retaining the accuracy of the atomistic model in the higher-scale model leads to remarkable breakthroughs in our understanding. The resulting atomistic model allows direct comparison with experimental techniques such as X-ray photoelectron spectroscopy and quartz crystal microbalance.

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.

Women's help seeking behaviour and the associated influencing factors on self discovery of a breast symptom

To investigate women’s help seeking behavior (HSB) following self discovery of a breast symptom and determine the associated influencing factors. A descriptive correlation design was used to ascertain the help seeking behavior (HSB) and the associated influencing factors of a sample of women (n = 449) with self discovered breast symptoms. The study was guided by the ‘Help Seeking Behaviour and Influencing Factors” conceptual framework (Facione et al., 2002; Meechan et al., 2003, 2002; Leventhal, Brissette and Leventhal, 2003 and O’Mahony and Hegarty, 2009b). Data was collected using a researcher developed multi-scale questionnaire package to ascertain women’s help seeking behavior on self discovery of a breast symptom and determine the factors most associated with HSB. Factors examined include: socio-demographics, knowledge and beliefs (regarding breast symptom; breast changes associated with breast cancer; use of alternative help seeking behaviours and presence or absence of a family history of breast cancer),emotional responses, social factors, health seeking habits and health service system utilization and help seeking behavior. A convenience sample (n = 449 was obtained by the researcher from amongst women attending the breast clinics of two large urban hospitals within the Republic of Ireland. All participants had self-discovered breast symptoms and no previous history of breast cancer. The study identified that while the majority of women (69.9%; n=314) sought help within one month, 30.1% (n=135) delayed help seeking for more than one month following self discovery of their breast symptom. The factors most significantly associated with HSB were the presenting symptom of ‘nipple indrawn/changes’ (p = 0.005), ‘ignoring the symptom and hoping it would go away’ (p < 0.001), the emotional response of being ‘afraid@ on symptom discovery (p = 0.005) and the perception/belief in longer symptom duration (p = 0.023). It was found that women who presented with an indrawn/changed nipple were more likely to delay (OR = 4.81) as were women who ‘ignored the symptoms and hoped it would go away’ (OR = 10.717). Additionally, the longer women perceived that their symptom would last, they more likely they were to delay (OR = 1.18). Conversely, being afraid following symptom discovery was associated with less delay (OR = 0.37; p=0.005). This study provides further insight into the HSB of women who self discovered breast symptoms. It highlights the complexity of the help seeking process, indicating that is not a linear event but is influenced by multiple factors which can have a significant impact on the outcomes in terms of whether women delay or seek help promptly. The study further demonstrates that delayed HSB persists amongst women with self discovered breast symptoms. This has important implications for continued emphasis on the promotion of breast awareness, prompt help seeking for self discovered breast symptoms and early detection and treatment of breast cancer, amongst women of all ages.

Variability in north temperate dung beetle assemblages at different spatial and temporal scales

This study examined the spatial and temporal variability of dung beetle assemblages across a variety of scales e.g. from the between-pad scale (examining the effects of dung size and type) to larger spatial scales encompassing southern Ireland. Dung beetle assemblage structure as sampled by dung pad cohort samples and dung baited pitfall trapping were compared. Generally, the rank order of abundance of dung beetle species was significantly correlated between pitfall catches and cohort pad samples. Across different dung sizes, in both pitfall catches and cohort pad samples, the relative abundance of species was frequently significantly different, but the rank order of abundance of dung beetle was usually significantly correlated. Considerable variations in pitfall catches at temporal scales of a few days appeared to be closely related to weather conditions and rotational grazing. However, despite considerable variation in absolute abundances between consecutive days of sampling, assemblage structure typically remained very similar. The relationship between dung pad size and dung beetle colonisation was investigated. In field experiments in which pads of different sizes (0.25 L, 0.5 L, 1.0 L and 1.5 L) were artificially deposited, there was a positive relationship between pad size and both biomass and number of beetles colonising dung pads and pitfall traps. In addition, with one exception, the field experiments indicated a general positive relationship between dung pad size and biomass density (dung beetle biomass per unit dung volume). A laboratory experiment indicated that pat residence times of A. rufipes were significantly correlated with dung pad size. Investigation of naturally-deposited cow dung pads in the field also indicated that both larval numbers and densities were significantly correlated with dung pad size. These results were discussed in the context of theory related to aggregation and coexistence of species, and resource utilisation by organisms in ephemeral, patchy resources. The colonisation by dung beetles of dung types from native herbivores (sheep, horse and cow) was investigated in field experiments. There were significant differences between the dung types in the chemical parameters measured, and there were significant differences in abundances of dung beetles colonising the dung types. Sheep dung was typically the preferred dung type. Data from these field experiments, and from published literature, indicated that dung beetle species can display dung type preferences, in terms of comparisons of both absolute and relative abundances. In addition, data from laboratory experiments indicate that both Aphodius larval production and pat residence times tended to be higher in those dung types which were preferred by adult Aphodius in the colonisation experiments. Data from dung-baited pitfall trapping (from this and another study) at several sites (up to 180 km distant) and over a number of years (between 1991 and 1996) were used to investigate spatial and temporal variation in dung beetle assemblage structure and composition (Aphodius, Sphaeridium and Geotrupes) across a range of scales in southern Ireland. Species richness levels, species composition and rank order of abundances were very similar between the assemblages. The temporal variability between seasons within any year exceeded temporal variability between years. DCA ordinations indicated that there was a similar level of variability between assemblage structure from the between-field (~1km) to regional (~180 km) spatial scales, and between year (6 years) temporal scales. At the biogeographical spatial scale, analysis of data from the literature indicated that there was considerable variability at this scale, largely due to species turnover.

Comparing impacts of new cropping systems on biodiversity in traditional rural China

This study selected six geographically-similar villages with traditional and alternative cultivation methods (two groups of three, one traditional and two alternatives) in two counties of Henan Province, China—a representative area of the Huang-huai-hai Plain representing traditional rural China. Soil heavy metal concentrations, floral and faunal biodiversity, and socio-economic data were recorded. Heavy metal concentrations of surface soils from three sites in each village were analysed using Inductively Coupled Plasma Mass Spectrometry (ICP-MS, chromium, nickel, copper, cadmium, and lead) and Atomic Absorption Spectrophotometer (AAS, zinc). The floral biodiversity of four land-use types was recorded following the Braun-Blanquet coverage-abundance method using 0.5×0.5m quadrats. The faunal biodiversity of two representative farmland plots was recorded using 0.3×0.3m quadrats at four 0.1m layers. The socio-economic data were recorded through face-to-face interviews of one hundred randomly selected households at each village. Results demonstrate different cultivation methods lead to different impact on above variables. Traditional cultivation led to lower heavy metal concentrations; both alternative managements were associated with massive agrochemical input causing heavy metal pollution in farmlands. Floral distribution was significantly affected by village factors. Diverse cultivation supported high floral biodiversity through multi-scale heterogeneous landscapes containing niches and habitats. Faunal distribution was also significantly affected by village factor nested within soil depth. Different faunal groups responded differently, with Acari being taxonomically diverse and Collembola high in densities. Increase in manual labour and crop number in villages using alternative cultivation may positively affect biodiversity. The results point to the conservation potential of diverse cultivation methods in traditional rural China and other regions under social and political reforms, where traditional agriculture is changing to unified, large-scale mechanized agriculture. This study serves as a baseline for conservation in small-holding agricultural areas of China, and points to the necessity of further studies at larger and longer scales.