Development and characterisation of solution processed vanadium oxide and transparent metal oxide thin films

Metal oxide thin films are important for modern electronic devices ranging from thin film transistors to photovoltaics and functional optical coatings. Solution processed techniques allow for thin films to be rapidly deposited over a range of surfaces without the extensive processing of comparative vapour or physical deposition methods. The production of thin films of vanadium oxide prepared through dip-coating was developed enabling a greater understanding of the thin film formation. Mechanisms of depositing improved large area uniform coverage on a number of technologically relevant substrates were examined. The fundamental mechanism for polymer-assisted deposition in improving thin film surface smoothness and long range order has been delivered. Different methods were employed for adapting the alkoxide based dip-coating technique to produce a variety of amorphous and crystalline vanadium oxide based thin films. Using a wide range of material, spectroscopic and optical measurement techniques the morphology, structure and optoelectronic properties of the thin films were studied. The formation of pinholes on the surface of the thin films, due to dewetting and spinodal effects, was inhibited using the polymer assisted deposition technique. Uniform thin films with sub 50 nm thicknesses were deposited on a variety of substrates controlled through alterations to the solvent-alkoxide dilution ratios and employing polymer assisted deposition techniques. The effects of polymer assisted deposition altered the crystallized VO thin films from a granular surface structure to a polycrystalline structure composed of high density small in-plane grains. The formation of transparent VO based thin film through Si and Na substrate mediated diffusion highlighted new methods for material formation and doping.

Kinetics and coverage dependent reaction mechanisms of the copper atomic layer deposition from copper dimethylamino-2-propoxide and diethylzinc

Atomic layer deposition (ALD) has been recognized as a promising method to deposit conformal and uniform thin film of copper for future electronic devices. However, many aspects of the reaction mechanism and the surface chemistry of copper ALD remain unclear. In this paper, we employ plane wave density functional theory (DFT) to study the transmetalation ALD reaction of copper dimethylamino-2-propoxide [Cu(dmap)2] and diethylzinc [Et2Zn] that was realized experimentally by Lee et al. [ Angew. Chem., Int. Ed. 2009, 48, 4536−4539]. We find that the Cu(dmap)2 molecule adsorbs and dissociates through the scission of one or two Cu–O bonds into surface-bound dmap and Cu(dmap) fragments during the copper pulse. As Et2Zn adsorbs on the surface covered with Cu(dmap) and dmap fragments, butane formation and desorption was found to be facilitated by the surrounding ligands, which leads to one reaction mechanism, while the migration of ethyl groups to the surface leads to another reaction mechanism. During both reaction mechanisms, ligand diffusion and reordering are generally endothermic processes, which may result in residual ligands blocking the surface sites at the end of the Et2Zn pulse, and in residual Zn being reduced and incorporated as an impurity. We also find that the nearby ligands play a cooperative role in lowering the activation energy for formation and desorption of byproducts, which explains the advantage of using organometallic precursors and reducing agents in Cu ALD. The ALD growth rate estimated for the mechanism is consistent with the experimental value of 0.2 Å/cycle. The proposed reaction mechanisms provide insight into ALD processes for copper and other transition metals.

Addressing non-linear hardware limitations and extending network coverage area for power aware wireless sensor networks

Science Foundation Ireland (07/CE/11147); Irish Research Council for Science Engineering and Technology (Embark Initiative)

Irish Times coverage of Irish relief and development nongovernmental organisations, legitimacy and accountability, 1994-2009: analysis and implications for the role of nongovernmental organisations

The overall aim of this study was to investigate the extent to which and ways in which Irish relief and development nongovernmental organisations (NGOs) were linked with the concepts of legitimacy and accountability in Irish Times newspaper coverage between 1994 and 2009. This research was based on a quantitative content analysis of 215 Irish Times articles and the results were analysed using statistical methods. Key findings of the research included that NGO accountability received significantly more coverage than NGO legitimacy, "principal-agent" approaches to NGO accountability received significantly more coverage than "stakeholder" approaches to NGO accountability, and questioning of NGOs based on either their accountability or legitimacy was very limited. It is suggested that these findings may indicate both a failure by Irish NGOs to promote "development literacy" and global solidarity among the Irish public, and a limited degree of "development literacy" and global solidarity among the Irish public.

Private health care coverage and increased risk of obstetric intervention

Background: When clinically indicated, common obstetric interventions can greatly improve maternal and neonatal outcomes. However, variation in intervention rates suggests that obstetric practice may not be solely driven by case criteria. Methods: Differences in obstetric intervention rates by private and public status in Ireland were examined using nationally representative hospital discharge data. A retrospective cohort study was performed on childbirth hospitalisations occurring between 2005 and 2010. Multivariate logistic regression analysis with correction for the relative risk was conducted to determine the risk of obstetric intervention (caesarean delivery, operative vaginal delivery, induction of labour or episiotomy) by private or public status while adjusting for obstetric risk factors. Results: 403,642 childbirth hospitalisations were reviewed; approximately one-third of maternities (30.2%) were booked privately. After controlling for relevant obstetric risk factors, women with private coverage were more likely to have an elective caesarean delivery (RR: 1.48; 95% CI: 1.45-1.51), an emergency caesarean delivery (RR: 1.13; 95% CI: 1.12-1.16) and an operative vaginal delivery (RR: 1.25; 95% CI: 1.22-1.27). Compared to women with public coverage who had a vaginal delivery, women with private coverage were 40% more likely to have an episiotomy (RR: 1.40; 95% CI: 1.38-1.43). Conclusions: Irrespective of obstetric risk factors, women who opted for private maternity care were significantly more likely to have an obstetric intervention. To better understand both clinical and non-clinical dynamics, future studies of examining health care coverage status and obstetric intervention would ideally apply mixed-method techniques.