The nature of alkanethiol self-assembled monolayer adsorption on sputtered gold substrates

A detailed study of the self-assembly and coverage by 1-nonanethiol of sputtered Au surfaces using molecular resolution atomic force microscopy (AFM) and scanning tunneling microscopy (STM) is presented. The monolayer self-assembles on a smooth Au surface composed predominantly of {111} oriented grains. The domains of the alkanethiol monolayer are observed with sizes typically of 5-25 nm, and multiple molecular domains can exist within one Au grain. STM imaging shows that the (4 × 2) superlattice structure is observed as a (3 × 2√3) structure when imaged under noncontact AFM conditions. The 1-nonanethiol molecules reside in the threefold hollow sites of the Au{111} lattice and aligned along its lattice vectors. The self-assembled monolayer (SAM) contains many nonuniformities such as pinholes, domain boundaries, and monatomic depressions which are present in the Au surface prior to SAM adsorption. The detailed observations demonstrate limitations to the application of 1-nonanethiol as a resist in atomic nanolithography experiments to feature sizes of ∼20 nm.

Study of the kinetics and mechanism of rapid self-assembly in block copolymer thin films during solvo-microwave annealing

Microwave annealing is an emerging technique for achieving ordered patterns of block copolymer films on substrates. Little is understood about the mechanisms of microphase separation during the microwave annealing process and how it promotes the microphase separation of the blocks. Here, we use controlled power microwave irradiation in the presence of tetrahydrofuran (THF) solvent, to achieve lateral microphase separation in high- lamellar-forming poly(styrene-b-lactic acid) PS-b-PLA. A highly ordered line pattern was formed within seconds on silicon, germanium and silicon on insulator (SOI) substrates. In-situ temperature measurement of the silicon substrate coupled to condition changes during "solvo-microwave" annealing allowed understanding of the processes to be attained. Our results suggest that the substrate has little effect on the ordering process and is essentially microwave transparent but rather, it is direct heating of the polar THF molecules that causes microphase separation. It is postulated that the rapid interaction of THF with microwaves and the resultant temperature increase to 55 degrees C within seconds causes an increase of the vapor pressure of the solvent from 19.8 to 70 kPa. This enriched vapor environment increases the plasticity of both PS and PLA chains and leads to the fast self-assembly kinetics. Comparing the patterns formed on silicon, germanium and silicon on insulator (SOI) and also an in situ temperature measurement of silicon in the oven confirms the significance of the solvent over the role of substrate heating during "solvo-microwave" annealing. Besides the short annealing time which has technological importance, the coherence length is on a micron scale and dewetting is not observed after annealing. The etched pattern (PLA was removed by an Ar/O-2 reactive ion etch) was transferred to the underlying silicon substrate fabricating sub-20 nm silicon nanowires over large areas demonstrating that the morphology is consistent both across and through the film.

Living long-term with acquired brain injury in Ireland: towards a counter discourse

Irish literature on Acquired Brain Injury (ABI) is very scant and is mainly deficits and/or needs based. The focus is generally on how to manage the short term needs of the younger population with ABI. The starting position of my thesis is that people living long-term with ABI are important participants in developing knowledge about this social phenomenon, living with ABI while accepting that their brain injury does not determine them. Six mature adults with ABI and their six significant others participated in this longitudinal study. Using a narrative approach in interviews, over twenty months, five repeat individual interviews with each of the twelve participants was held. From this I gained an understanding of their lived experiences, their life-world and their experiences of our local public ABI/disability services, systems and discourse. Along with this new empirical data, theoretical developments from occupational therapy, occupational science, sociology, and disability studies were also used within a meta-narrative informed by critical theory and critical realism to develop a synthesis of this study. Social analysis of their narratives co-constructed with me, allowed me generate nuanced insights into tendencies and social processes that impacted and continues to impact on their everyday-everynight living. I discuss in some depth here, the relational attitudinal, structural, occupational and environmental supports, barriers or discrimination that they face(d) in their search for social participation and community inclusion. Personal recognition of the disabled participants by their family, friends and/or local community, was generally enhanced after much suffering, social supports, slow recovery, and with some form of meaningful occupational engagement. This engagement was generally linked with pre-injury interests or habits, while Time itself became both a major aid and a need. The present local ABI discourse seldom includes advocacy and inclusion in everyday/every night local events, yet most participants sought both peer-support or collective recognition, and social/community inclusion to help develop their own counter-discourse to the dominant ABI discourse. This thesis aims to give a broad social explanation on aspects of their social becoming, 'self-sameness' and social participation, and the status of the disabled participants wanting to live 'the slow life'. Tensions and dialectical issues involved in moving from the category of a person in coma, to person with a disability, to being a citizen should not demote the need for special services. While individualized short-term neuro-rehabilitation is necessary, it is not sufficient. Along with the participants, this researcher asks that community health and/or social care planners and service-providers rethink how ABI is understood and represented, and how people with ABI are included in their local communities

Covert conversations: disciplined improvisation and meaning-making in the masters (MA) supervisory relationship

This research asks the question: “What are the relational dynamics in Masters (MA) supervision?” It does so by focusing upon the supervisory relationship itself. It does this through dialoguing with the voices of both MA supervisors and supervisees in the Humanities using a Cultural Historical Activity Theory (CHAT) framework. In so doing, this research argues for a re-evaluation of how MA supervision is conceptualised and proposes a new theoretical framework for conceptualising MA supervision as a relational phenomenon. The research design was derived from an Activity Theory-influenced methodology. Data collection procedures included the administration of Activity Theory Logs, individual semi-structured interviews with both supervisors and supervisees and the completion of reflective journals. Grounded Theory was used to analyse the data. The sample for the study consists of three supervisor-supervisee dyads from three disciplines in the Humanities. Data was collected over the course of one academic year, 2010-2011. This research found that both individual and shared relational dynamics play an important role in MA supervision. Individual dynamics, such as supervisors’ iterative negotiation of ambiguity/clarity and supervisees’ boundary work, revealed that both parties attempt to negotiate a separation between their professional-academic identities and personal identities. However, an inherent paradox emerged when the shared relational dynamics of MA supervision were investigated. It was found that the shared space created by the supervisory relationship did not only exist in a physical setting, but was also psychoactive in nature and held strong emotional resonances for both parties involved. This served to undermine the separation between professional-academic and personal identities. As a result, this research argues that the interaction between the individual and shared relational dynamics in MA supervision enables, for both supervisors and supervisees, a disciplined improvisation of academic identity.

In-situ examination of the selective etching of an alkanethiol monolayer covered Au{111} surface

An examination of the selective etching mechanism of a 1-alkanethiol self-assembled monolayer (SAM) covered Au{111} surface using in-situ atomic force microscopy (AFM) and molecular resolution scanning tunnelling microscopy (STM) is presented. The monolayer self-assembles on a smooth Au{111} surface and typically contains nanoscale non-uniformities such as pinholes, domain boundaries and monatomic depressions. During etching in a ferri/ferrocyanide water-based etchant, selective and preferential etching occurs at SAM covered Au(111) terrace and step edges where a lower SAM packing density is observed, resulting in triangular islands being relieved. The triangular islands are commensurate with the Au(111) lattice with their long edges parallel to its [11-0] direction. Thus, SAM etching is selective and preferential attack is localized to defects and step edges at sites of high molecular density contrast.

Risk of repeated self-harm and associated factors in children, adolescents and young adults

Background: Repeated self-harm represents the single strongest risk factor for suicide. To date no study with full national coverage has examined the pattern of hospital repeated presentations due to self-harm among young people. Methods: Data on consecutive self-harm presentations were obtained from the National Self-Harm Registry Ireland. Socio-demographic and behavioural characteristics of individuals aged 10–29 years who presented with self-harm to emergency departments in Ireland (2007–2014) were analysed. Risk of long-term repetition was assessed using survival analysis and time differences between the order of presentations using generalised estimating equation analysis. Results: The total sample comprised 28,700 individuals involving 42,642 presentations. Intentional drug overdose was the most prevalent method (57.9%). Repetition of self-harm occurred in 19.2% of individuals during the first year following a first presentation, of whom the majority (62.7%) engaged in one repeated act. Overall, the risk of repeated self-harm was similar between males and females. However, in the 20–24-year-old age group males were at higher risk than females. Those who used self-cutting were at higher risk for repetition than those who used intentional drug overdose, particularly among females. Age was associated with repetition only among females, in particular adolescents (15–19 years old) were at higher risk than young emerging adults (20–24 years old). Repeated self-harm risk increased significantly with the number of previous self-harm episodes. Time differences between first self-harm presentations were detected. Time between second and third presentation increased compared to time between first and second presentation among low frequency repeaters (patients with 3 presentations only within 1 year following a first presentation). The same time period decreased among high frequency repeaters (patients with at least 4 to more than 30 presentations). Conclusion: Young people with the highest risk for repeated self-harm were 15–19-year-old females and 20–24-year-old males. Self-cutting was the method associated with the highest risk of self-harm repetition. Time between first self-harm presentations represents an indicator of subsequent repetition. To prevent risk of repeated self-harm in young people, all individuals presenting at emergency departments due to self-harm should be provided with a risk assessment including psychosocial characteristics, history of self-harm and time between first presentations.

Semiconductor nanowire fabrication via bottom-up & top-down paradigms

Semiconductor nanowires are pseudo 1-D structures where the magnitude of the semiconducting material is confined to a length of less than 100 nm in two dimensions. Semiconductor nanowires have a vast range of potential applications, including electronic (logic devices, diodes), photonic (laser, photodetector), biological (sensors, drug delivery), energy (batteries, solar cells, thermoelectric generators), and magnetic (spintronic, memory) devices. Semiconductor nanowires can be fabricated by a range of methods which can be categorised into one of two paradigms, bottom-up or top-down. Bottom-up processes can be defined as those where structures are assembled from their sub-components in an additive fashion. Top-down fabrication strategies use sculpting or etching to carve structures from a larger piece of material in a subtractive fashion. This seminar will detail a number of novel routes to fabricate semiconductor nanowires by both bottom-up and top-down paradigms. Firstly, a novel bottom-up route to fabricate Ge nanowires with controlled diameter distributions in the sub-20 nm regime will be described. This route details nanowire synthesis and diameter control in the absence of a foreign seed metal catalyst. Additionally a top-down route to nanowire array fabrication will be detailed outlining the importance of surface chemistry in high-resolution electron beam lithography (EBL) using hydrogen silsesquioxane (HSQ) on Ge and Bi2Se3 surfaces. Finally, a process will be described for the directed self-assembly of a diblock copolymer (PS-b-PDMS) using an EBL defined template. This section will also detail a route toward selective template sidewall wetting of either block in the PS-b-PDMS system, through tailored functionalisation of the template and substrate surfaces.

Energy storage systems for wave energy converters and microgrids

The thesis initially gives an overview of the wave industry and the current state of some of the leading technologies as well as the energy storage systems that are inherently part of the power take-off mechanism. The benefits of electrical energy storage systems for wave energy converters are then outlined as well as the key parameters required from them. The options for storage systems are investigated and the reasons for examining supercapacitors and lithium-ion batteries in more detail are shown. The thesis then focusses on a particular type of offshore wave energy converter in its analysis, the backward bent duct buoy employing a Wells turbine. Variable speed strategies from the research literature which make use of the energy stored in the turbine inertia are examined for this system, and based on this analysis an appropriate scheme is selected. A supercapacitor power smoothing approach is presented in conjunction with the variable speed strategy. As long component lifetime is a requirement for offshore wave energy converters, a computer-controlled test rig has been built to validate supercapacitor lifetimes to manufacturer’s specifications. The test rig is also utilised to determine the effect of temperature on supercapacitors, and determine application lifetime. Cycle testing is carried out on individual supercapacitors at room temperature, and also at rated temperature utilising a thermal chamber and equipment programmed through the general purpose interface bus by Matlab. Application testing is carried out using time-compressed scaled-power profiles from the model to allow a comparison of lifetime degradation. Further applications of supercapacitors in offshore wave energy converters are then explored. These include start-up of the non-self-starting Wells turbine, and low-voltage ride-through examined to the limits specified in the Irish grid code for wind turbines. These applications are investigated with a more complete model of the system that includes a detailed back-to-back converter coupling a permanent magnet synchronous generator to the grid. Supercapacitors have been utilised in combination with battery systems for many applications to aid with peak power requirements and have been shown to improve the performance of these energy storage systems. The design, implementation, and construction of coupling a 5 kW h lithium-ion battery to a microgrid are described. The high voltage battery employed a continuous power rating of 10 kW and was designed for the future EV market with a controller area network interface. This build gives a general insight to some of the engineering, planning, safety, and cost requirements of implementing a high power energy storage system near or on an offshore device for interface to a microgrid or grid.

Synthesis & characterisation of group IV semiconducting nanowires

Semiconductor nanowires, particularly group 14 semiconductor nanowires, have been the subject of intensive research in the recent past. They have been demonstrated to provide an effective, versatile route towards the continued miniaturisation and improvement of microelectronics. This thesis aims to highlight some novel ways of fabricating and controlling various aspects of the growth of Si and Ge nanowires. Chapter 1 highlights the primary technique used for the growth of nanowires in this study, namely, supercritical fluid (SCF) growth reactions. The advantages (and disadvantages) of this technique for the growth of Si and Ge nanowires are highlighted, citing numerous examples from the past ten years. The many variables involved in this technique are discussed along with the resultant characteristics of nanowires produced (diameter, doping, orientation etc.). Chapter 2 outlines the experimental methodologies used in this thesis. The analytical techniques used for the structural characterisation of nanowires produced are also described as well as the techniques used for the chemical analysis of various surface terminations. Chapter 3 describes the controlled self-seeded growth of highly crystalline Ge nanowires, in the absence of conventional metal seed catalysts, using a variety of oligosilylgermane precursors and mixtures of germane and silane compounds. A model is presented which describes the main stages of self-seeded Ge nanowire growth (nucleation, coalescence and Ostwald ripening) from the oligosilylgermane precursors and in conjunction with TEM analysis, a mechanism of growth is proposed. Chapter 4 introduces the metal assisted etching (MAE) of Si substrates to produce Si nanowires. A single step metal-assisted etch (MAE) process, utilising metal ion-containing HF solutions in the absence of an external oxidant, was developed to generate heterostructured Si nanowires with controllable porous (isotropically etched) and non-porous (anisotropically etched) segments. In Chapter 5 the bottom-up growth of Ge nanowires, similar to that described in Chapter 3, and the top down etching of Si, described in Chapter 4, are combined. The introduction of a MAE processing step in order to “sink” the Ag seeds into the growth substrate, prior to nanowire growth, is shown to dramatically decrease the mean nanowire diameters and to narrow the diameter distributions. Finally, in Chapter 6, the biotin – streptavidin interaction was explored for the purposes of developing a novel Si junctionless nanowire transistor (JNT) sensor.

Pyramidal quantum dots: single and entangled photon sources and correlation studies

Practical realisation of quantum information science is a challenge being addressed by researchers employing various technologies. One of them is based on quantum dots (QD), usually referred to as artificial atoms. Being capable to emit single and polarization entangled photons, they are attractive as sources of quantum bits (qubits) which can be relatively easily integrated into photonic circuits using conventional semiconductor technologies. However, the dominant self-assembled QD systems suffer from asymmetry related problems which modify the energetic structure. The main issue is the degeneracy lifting (the fine-structure splitting, FSS) of an optically allowed neutral exciton state which participates in a polarization-entanglement realisation scheme. The FSS complicates polarization-entanglement detection unless a particular FSS manipulation technique is utilized to reduce it to vanishing values, or a careful selection of intrinsically good candidates from the vast number of QDs is carried out, preventing the possibility of constructing vast arrays of emitters on the same sample. In this work, site-controlled InGaAs QDs grown on (111)B oriented GaAs substrates prepatterned with 7.5 μm pitch tetrahedrons were studied in order to overcome QD asymmetry related problems. By exploiting an intrinsically high rotational symmetry, pyramidal QDs were shown as polarization-entangled photon sources emitting photons with the fidelity of the expected maximally entangled state as high as 0.721. It is the first site-controlled QD system of entangled photon emitters. Moreover, the density of such emitters was found to be as high as 15% in some areas: the density much higher than in any other QD system. The associated physical phenomena (e.g., carrier dynamic, QD energetic structure) were studied, as well, by different techniques: photon correlation spectroscopy, polarization-resolved microphotoluminescence and magneto-photoluminescence.

States of play: Irish childhoods, race and belonging

This thesis explores the meaning-making practices of migrant and non-migrant children in relation to identities, race, belonging and childhood itself in their everyday lives and in the context of ‘normalizing’ discourses and spaces in Ireland. The relational, spatial and institutional contexts of children’s worlds are examined in the arenas of school, home, family, peer groups and consumer culture. The research develops a situated account of children’s complex subject positions, belongings and exclusions, as negotiated within discursive constructs, emerging in the ‘in-between’ spaces explored with other children and with adults. As a peripheral EU area both geographically and economically, Ireland has traditionally been a country of net emigration. This situation changed briefly in the late 1990s to early 2000s, sparking broad debate on Ireland’s perceived ‘new’ ethnic, cultural and linguistic diversity arising from the arrival of migrant people both from within and beyond the EU as workers and as asylum seekers, and drawing attention to issues of race, identity, equality and integration in Irish society. Based in a West of Ireland town where migrant children and children of migrants comprise very small minorities in classroom settings, this research engages with a particular demographic of children who have started primary school since these changes have occurred. It seeks to represent the complexities of the processes which constitute children’s subjectivities, and which also produce and reproduce race and childhood itself in this context. The role of local, national and global spaces, relational networks and discursive currents as they are experienced and negotiated by children are explored, and the significance of embodied, sensory and affective processes are integrated into the analysis. Notions of the functions and rhetorics of play and playfulness (Sutton-Smith 1997) form a central thread that runs throughout the thesis, where play is both a feature of children’s cultural worlds and a site of resistance or ‘thinking otherwise’. The study seeks to examine how children actively participate in (re)producing definitions of both childhood and race arising in local, national and global spaces, demonstrating that while contestations of the boundaries of childhood discourses are contingently successful, race tends to be strongly reiterated, clinging to bodies and places and compromising belonging. In addition, it explores how children access belongings through agentic and imaginative practices with regard to peer and family relationships, particularly highlighting constructions of home, while also illustrating practices of excluding children positioned as unintelligible, including the role of silences in such situations. Finally, drawing on teachers’ understandings and on children’s playful micro-level negotiations of race, the study argues that assumptions of childhood innocence contribute to justifying depoliticised discourses of race in the early primary school years, and also tend to silence children’s own dialogues with this issue. Central throughout the thesis is an emphasis on the productive potentials of children’s marginal positioning in processes of transgressing definitional boundaries, including the generation of post-race conceptualisations that revealed the borders of race as performative and fluid. It suggests that interrupting exclusionary raced identities in Irish primary schools requires engagement with children’s world-making practices and the multiple resources that inform their lives.