Procurement of electronic content across the UK National Health Service and Higher Education sectors. Report to JISC executive and LKDN executive.

Spink, S., Urquhart, C., Cox, A. & Higher Education Academy - Information and Computer Sciences Subject Centre. (2007). Procurement of electronic content across the UK National Health Service and Higher Education sectors. Report to JISC executive and LKDN executive. Sponsorship: JISC/LKDN

Collaboration on procurement of e-content between the National Health Service and higher education in the UK

Urquhart, C. J., Cox, A. M.& Spink, S. (2007). Collaboration on procurement of e-content between the National Health Service and higher education in the UK. Interlending & Document Supply, 35(3), 164-170. Sponsorship: JISC, LKDN

Best practices for competency development and assessment in higher education

The main objective of this article is to present the results of a study aimed at determining, classifying and evaluating practices of interest for general competency development and assessment in undergraduate programmes. The study encompassed the following phases: (1) focus group in order to establish a starting point regarding competency development and assessment, counting on the opinion of some of the best-rated teachers belonging to the participating universities; (2) collection of best practices; (3) design and validation of a scale for the assessment of best practices; and (4) scale administration (evaluation of good practices) and data analysis.

Optical determination of fractal dimensions using Fourier transforms

R. Zwiggelaar and C.R. Bull, 'Optical determination of fractal dimensions using Fourier transforms', Optical Engineering 34 (5), 1325-1332 (1995)

Examining the Aesthetic Dimensions of the Constitutional Treaty

Gibbs, Nathan, Examining the Aesthetic Dimensions of the Constitutional Treaty. European Law Journal, Vol. 11, No. 3, pp. 326-342, May 2005 RAE2008

Business service quality in an e-commerce environment

Yang, Y., Humphreys, P., & McIvor, R. (2006). Business service quality in an e-commerce environment. Supply Chain Management: An International Journal, 11 (3), 195-201. RAE2008

Avaliação da qualidade de serviço

Dissertação de Mestrado apresentada à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Gestão da Qualidade.

Qualidade de Vida, Vinculação e Resiliência em adolescentes institucionalizados

Dissertação apresentada à Universidade Fernando Pessoa como parte dos requisitos para a obtenção do grau de Mestre em Psicologia, ramo de Psicologia Clínica e da Saúde

SEP: A Stable Election Protocol for clustered heterogeneous wireless sensor networks

We study the impact of heterogeneity of nodes, in terms of their energy, in wireless sensor networks that are hierarchically clustered. In these networks some of the nodes become cluster heads, aggregate the data of their cluster members and transmit it to the sink. We assume that a percentage of the population of sensor nodes is equipped with additional energy resources-this is a source of heterogeneity which may result from the initial setting or as the operation of the network evolves. We also assume that the sensors are randomly (uniformly) distributed and are not mobile, the coordinates of the sink and the dimensions of the sensor field are known. We show that the behavior of such sensor networks becomes very unstable once the first node dies, especially in the presence of node heterogeneity. Classical clustering protocols assume that all the nodes are equipped with the same amount of energy and as a result, they can not take full advantage of the presence of node heterogeneity. We propose SEP, a heterogeneous-aware protocol to prolong the time interval before the death of the first node (we refer to as stability period), which is crucial for many applications where the feedback from the sensor network must be reliable. SEP is based on weighted election probabilities of each node to become cluster head according to the remaining energy in each node. We show by simulation that SEP always prolongs the stability period compared to (and that the average throughput is greater than) the one obtained using current clustering protocols. We conclude by studying the sensitivity of our SEP protocol to heterogeneity parameters capturing energy imbalance in the network. We found that SEP yields longer stability region for higher values of extra energy brought by more powerful nodes.

Forewarding in Mobile Opportunistic Networks

Recent advances in processor speeds, mobile communications and battery life have enabled computers to evolve from completely wired to completely mobile. In the most extreme case, all nodes are mobile and communication takes place at available opportunities – using both traditional communication infrastructure as well as the mobility of intermediate nodes. These are mobile opportunistic networks. Data communication in such networks is a difficult problem, because of the dynamic underlying topology, the scarcity of network resources and the lack of global information. Establishing end-to-end routes in such networks is usually not feasible. Instead a store-and-carry forwarding paradigm is better suited for such networks. This dissertation describes and analyzes algorithms for forwarding of messages in such networks. In order to design effective forwarding algorithms for mobile opportunistic networks, we start by first building an understanding of the set of all paths between nodes, which represent the available opportunities for any forwarding algorithm. Relying on real measurements, we enumerate paths between nodes and uncover what we refer to as the path explosion effect. The term path explosion refers to the fact that the number of paths between a randomly selected pair of nodes increases exponentially with time. We draw from the theory of epidemics to model and explain the path explosion effect. This is the first contribution of the thesis, and is a key observation that underlies subsequent results. Our second contribution is the study of forwarding algorithms. For this, we rely on trace driven simulations of different algorithms that span a range of design dimensions. We compare the performance (success rate and average delay) of these algorithms. We make the surprising observation that most algorithms we consider have roughly similar performance. We explain this result in light of the path explosion phenomenon. While the performance of most algorithms we studied was roughly the same, these algorithms differed in terms of cost. This prompted us to focus on designing algorithms with the explicit intent of reducing costs. For this, we cast the problem of forwarding as an optimal stopping problem. Our third main contribution is the design of strategies based on optimal stopping principles which we refer to as Delegation schemes. Our analysis shows that using a delegation scheme reduces cost over naive forwarding by a factor of O(√N), where N is the number of nodes in the network. We further validate this result on real traces, where the cost reduction observed is even greater. Our results so far include a key assumption, which is unbounded buffers on nodes. Next, we relax this assumption, so that the problem shifts to one of prioritization of messages for transmission and dropping. Our fourth contribution is the study of message prioritization schemes, combined with forwarding. Our main result is that one achieves higher performance by assigning higher priorities to young messages in the network. We again interpret this result in light of the path explosion effect.

Police accountability in Ireland: an analysis of the problems posed by the legal, constitutional and political dimensions and how they might be addressed

The concept of police accountability is not susceptible to a universal or concise definition. In the context of this thesis it is treated as embracing two fundamental components. First, it entails an arrangement whereby an individual, a minority and the whole community have the opportunity to participate meaningfully in the formulation of the principles and policies governing police operations. Second, it presupposes that those who have suffered as victims of unacceptable police behaviour should have an effective remedy. These ingredients, however, cannot operate in a vacuum. They must find an accommodation with the equally vital requirement that the burden of accountability should not be so demanding that the delivery of an effective police service is fatally impaired. While much of the current debate on police accountability in Britain and the USA revolves around the issue of where the balance should be struck in this accommodation, Ireland lacks the very foundation for such a debate as it suffers from a serious deficit in research and writing on police generally. This thesis aims to fill that gap by laying the foundations for an informed debate on police accountability and related aspects of police in Ireland. Broadly speaking the thesis contains three major interrelated components. The first is concerned with the concept of police in Ireland and the legal, constitutional and political context in which it operates. This reveals that although the Garda Siochana is established as a national force the legal prescriptions concerning its role and governance are very vague. Although a similar legislative format in Britain, and elsewhere, have been interpreted as conferring operational autonomy on the police it has not stopped successive Irish governments from exercising close control over the police. The second component analyses the structure and operation of the traditional police accountability mechanisms in Ireland; namely the law and the democratic process. It concludes that some basic aspects of the peculiar legal, constitutional and political structures of policing seriously undermine their capacity to deliver effective police accountability. In the case of the law, for example, the status of, and the broad discretion vested in, each individual member of the force ensure that the traditional legal actions cannot always provide redress where individuals or collective groups feel victimised. In the case of the democratic process the integration of the police into the excessively centralised system of executive government, coupled with the refusal of the Minister for Justice to accept responsibility for operational matters, project a barrier between the police and their accountability to the public. The third component details proposals on how the current structures of police accountability in Ireland can be strengthened without interfering with the fundamentals of the law, the democratic process or the legal and constitutional status of the police. The key elements in these proposals are the establishment of an independent administrative procedure for handling citizen complaints against the police and the establishment of a network of local police-community liaison councils throughout the country coupled with a centralised parliamentary committee on the police. While these proposals are analysed from the perspective of maximising the degree of police accountability to the public they also take into account the need to ensure that the police capacity to deliver an effective police service is not unduly impaired as a result.

Preparation and characterisation of ceria particles

Cerium dioxide (ceria) nanoparticles have been the subject of intense academic and industrial interest. Ceria has a host of applications but academic interest largely stems from their use in the modern automotive catalyst but it is also of interest because of many other application areas notably as the abrasive in chemical-mechanical planarisation of silicon substrates. Recently, ceria has been the focus of research investigating health effects of nanoparticles. Importantly, the role of non-stoichiometry in ceria nanoparticles is implicated in their biochemistry. Ceria has well understood non-stoichiometry based around the ease of formation of anion vacancies and these can form ordered superstructures based around the fluorite lattice structure exhibited by ceria. The anion vacancies are associated with localised or small polaron states formed by the electrons that remain after oxygen desorption. In simple terms these electrons combine with Ce4+ states to form Ce3+ states whose larger ionic radii is associated with a lattice expansion compared to stoichiometric CeO2. This is a very simplistic explanation and greater defect chemistry complexity is suggested by more recent work. Various authors have shown that vacancies are mobile and may result in vacancy clustering. Ceria nanoparticles are of particular interest because of the high activity and surface area of small particulates. The sensitivity of the cerium electronic band structure to environment would suggest that changes in the properties of ceria particles at nanoscale dimensions might be expected. Notably many authors report a lattice expansion with reducing particle size (largely confined to sub-10 nm particles). Most authors assign increased lattice dimensions to the presence of a surface stable Ce2O3 type layer at low nanoparticle dimensions. However, our understanding of oxide nanoparticles is limited and their full and quantitative characterisation offers serious challenges. In a series of chemical preparations by ourselves we see little evidence of a consistent model emerging to explain lattice parameter changes with nanoparticle size. Based on these results and a review of the literature it is worthwhile asking if a model of surface enhanced defect concentration is consistent with known cerium/cerium oxide chemistries, whether this is applicable to a range of different synthesis methods and if a more consistent description is possible. In Chapter one the science of cerium oxide is outlined including the crystal structure, defect chemistry and different oxidation states available. The uses and applications of cerium oxide are also discussed as well as modelling of the lattice parameter and the doping of the ceria lattice. Chapter two describes both the synthesis techniques and the analytical methods employed to execute this research. Chapter three focuses on high surface area ceria nano-particles and how these have been prepared using a citrate sol-gel precipitation method. Changes to the particle size have been made by calcining the ceria powders at different temperatures. X-ray diffraction methods were used to determine their lattice parameters. The particles sizes were also assessed using transmission electron microscopy (TEM), scanning electron microscopy (SEM), and BET, and, the lattice parameter was found to decrease with decreasing particle size. The results are discussed in light of the role played by surface tension effects. Chapter four describes the morphological and structural characterization of crystalline CeO2 nanoparticles prepared by forward and reverse precipitation techniques and compares these by powder x-ray diffraction (PXRD), nitrogen adsorption (BET) and high resolution transmission electron microscopy (HRTEM) analysis. The two routes give quite different materials although in both cases the products are essentially highly crystalline, dense particulates. It was found that the reverse precipitation technique gave the smallest crystallites with the narrowest size dispersion. This route also gave as-synthesised materials with higher surface areas. HRTEM confirmed the observations made from PXRD data and showed that the two methods resulted in quite different morphologies and surface chemistries. The forward route gives products with significantly greater densities of Ce3+ species compared to the reverse route. Data are explained using known precipitation chemistry and kinetic effects. Chapter five centres on the addition of terbia to ceria and has been investigated using XRD, XRF, XPS and TEM. Good solid solutions were formed across the entire composition range and there was no evidence for the formation of mixed phases or surface segregation over either the composition or temperature range investigated. Both Tb3+ and Tb4+ ions exist within the solution and the ratios of these cations are consistent with the addition of Tb8O15 to the fluorite ceria structure across a wide range of compositions. Local regions of anion vacancy ordering may be visible for small crystallites. There is no evidence of significant Ce3+ ion concentrations formed at the surface or in the bulk by the addition of terbia. The lattice parameter of these materials was seen to decrease with decreasing crystallite size. This is consistent with increased surface tension effects at small dimension. Chapter six reviews size related lattice parameter changes and surface defects in ceria nanocrystals. Ceria (CeO2) has many important applications, notably in catalysis. Many of its uses rely on generating nanodimensioned particles. Ceria has important redox chemistry where Ce4+ cations can be reversibly reduced to Ce3+ cations and associated anion vacancies. The significantly larger size of Ce3+ (compared with Ce4+) has been shown to result in lattice expansion. Many authors have observed lattice expansion in nanodimensioned crystals (nanocrystals), and these have been attributed to the presence of stabilized Ce3+ -anion vacancy combinations in these systems. Experimental results presented here show (i) that significant, but complex changes in the lattice parameter with size can occur in 2-500 nm crystallites, (ii) that there is a definitive relationship between defect chemistry and the lattice parameter in ceria nanocrystals, and (iii) that the stabilizing mechanism for the Ce3+ -anion vacancy defects at the surface of ceria nanocrystals is determined by the size, the surface status, and the analysis conditions. In this work, both lattice expansion and a more unusual lattice contraction in ultrafine nanocrystals are observed. The lattice deformations seen can be defined as a function of both the anion vacancy (hydroxyl) concentration in the nanocrystal and the intensity of the additional pressure imposed by the surface tension on the crystal. The expansion of lattice parameters in ceria nanocrystals is attributed to a number of factors, most notably, the presence of any hydroxyl moieties in the materials. Thus, a very careful understanding of the synthesis combined with characterization is required to understand the surface chemistry of ceria nanocrystals.

Simulation of multigate SOI transistors with silicon, germanium and III-V channels

In this work by employing numerical three-dimensional simulations we study the electrical performance and short channel behavior of several multi-gate transistors based on advanced SOI technology. These include FinFETs, triple-gate and gate-all-around nanowire FETs with different channel material, namely Si, Ge, and III-V compound semiconductors, all most promising candidates for future nanoscale CMOS technologies. Also, a new type of transistor called “junctionless nanowire transistor” is presented and extensive simulations are carried out to study its electrical characteristics and compare with the conventional inversion- and accumulation-mode transistors. We study the influence of device properties such as different channel material and orientation, dimensions, and doping concentration as well as quantum effects on the performance of multi-gate SOI transistors. For the modeled n-channel nanowire devices we found that at very small cross sections the nanowires with silicon channel are more immune to short channel effects. Interestingly, the mobility of the channel material is not as significant in determining the device performance in ultrashort channels as other material properties such as the dielectric constant and the effective mass. Better electrostatic control is achieved in materials with smaller dielectric constant and smaller source-to-drain tunneling currents are observed in channels with higher transport effective mass. This explains our results on Si-based devices. In addition to using the commercial TCAD software (Silvaco and Synopsys TCAD), we have developed a three-dimensional Schrödinger-Poisson solver based on the non-equilibrium Green’s functions formalism and in the framework of effective mass approximation. This allows studying the influence of quantum effects on electrical performance of ultra-scaled devices. We have implemented different mode-space methodologies in our 3D quantum-mechanical simulator and moreover introduced a new method to deal with discontinuities in the device structures which is much faster than the coupled-mode-space approach.

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.

Fabrication and characterisation of semiconductor nanowires and metal interconnects

One-dimensional semiconductor nanowires are considered to be promising materials for future nanoelectronic applications. However, before these nanowires can be integrated into such applications, a thorough understanding of their growth behaviour is necessary. In particular, methods that allow the control over nanowire growth are deemed especially important as it is these methods that will enable the control of nanowire dimensions such as length and diameter (high aspect ratios). The production of nanowires with high-aspect ratios is vital in order to take advantage of the unique properties experienced at the nanoscale, thus allowing us to maximise their use in devices. Additionally, the development of low-resistivity interconnects is desirable in order to connect such nanowires in multi-nanowire components. Consequently, this thesis aims to discuss the synthesis and characterisation of germanium (Ge) nanowires and platinum (Pt) interconnects. Particular emphasis is placed on manipulating the nanowire growth kinetics to produce high aspect ratio structures. The discussion of Pt interconnects focuses on the development of low-resistivity devices and the electrical and structural analysis of those devices. Chapter 1 reviews the most critical aspects of Ge nanowire growth which must be understood before they can be integrated into future nanodevices. These features include the synthetic methods employed to grow Ge nanowires, the kinetic and thermodynamic aspects of their growth and nanowire morphology control. Chapter 2 outlines the experimental methods used to synthesise and characterise Ge nanowires as well as the methods used to fabricate and analyse Pt interconnects. Chapter 3 discusses the control of Ge nanowire growth kinetics via the manipulation of the supersaturation of Ge in the Au/Ge binary alloy system. This is accomplished through the use of bi-layer films, which pre-form Au/Ge alloy catalysts before the introduction of the Ge precursor. The growth from these catalysts is then compared with Ge nanowire growth from standard elemental Au seeds. Nanowires grown from pre-formed Au/Ge alloy seeds demonstrate longer lengths and higher growth rates than those grown from standard Au seeds. In-situ TEM heating on the Au/Ge bi-layer films is used to support the growth characteristics observed. Chapter 4 extends the work of chapter 3 by utilising Au/Ag/Ge tri-layer films to enhance the growth rates and lengths of Ge nanowires. These nanowires are grown from Au/Ag/Ge ternary alloy catalysts. Once again, the supersaturation is influenced, only this time it is through the simultaneous manipulation of both the solute concentration and equilibrium concentration of Ge in the Au/Ag/Ge ternary alloy system. The introduction of Ag to the Au/Ge binary alloy lowers the equilibrium concentration, thus increasing the nanowire growth rate and length. Nanowires with uniform diameters were obtained via synthesis from AuxAg1-x alloy nanoparticles. Manifestation of the Gibbs-Thomson effect, resulting from the dependence of the mean nanowire length as a function of diameter, was observed for all of the nanowires grown from the AuxAg1-x nanoparticles. Finally, in-situ TEM heating was used to support the nanowire growth characteristics. Chapter 5 details the fabrication and characterisation of Pt interconnects deposited by electron beam induced deposition of two different precursors. The fabrication is conducted inside a dual beam FIB. The electrical and structural characteristics of interconnects deposited from a standard organometallic precursor and a novel carbon-free precursor are compared. The electrical performance of the carbon-free interconnects is shown to be superior to that of the organometallic devices and this is correlated to the structural composition of both interconnects via in-situ TEM heating and HAADF-STEM analysis. Annealing of the interconnects is carried out under two different atmospheres in order to reduce the electrical resistivity even further. Finally, chapter 6 presents some important conclusions and summarises each of the previous chapters.