Direct measurement of coherency limits for strain relaxation in heteroepitaxial core/shell nanowires

The growth of heteroepitaxially strained semiconductors at the nanoscale enables tailoring of material properties for enhanced device performance. For core/shell nanowires (NWs), theoretical predictions of the coherency limits and the implications they carry remain uncertain without proper identification of the mechanisms by which strains relax. We present here for the Ge/Si core/shell NW system the first experimental measurement of critical shell thickness for strain relaxation in a semiconductor NW heterostructure and the identification of the relaxation mechanisms. Axial and tangential strain relief is initiated by the formation of periodic a/2 〈110〉 perfect dislocations via nucleation and glide on {111} slip-planes. Glide of dislocation segments is directly confirmed by real-time in situ transmission electron microscope observations and by dislocation dynamics simulations. Further shell growth leads to roughening and grain formation which provides additional strain relief. As a consequence of core/shell strain sharing in NWs, a 16 nm radius Ge NW with a 3 nm Si shell is shown to accommodate 3% coherent strain at equilibrium, a factor of 3 increase over the 1 nm equilibrium critical thickness for planar Si/Ge heteroepitaxial growth. © 2012 American Chemical Society.

Annealing and temperature coefficient study of type IA fibre Bragg gratings inscribed under strain and no strain - Implications to optical fibre component reliability

The annealing properties of Type IA Bragg gratings are investigated and compared with Type I and Type IIA Bragg gratings. The transmission properties (mean and modulated wavelength components) of gratings held at predetermined temperatures are recorded from which decay characteristics are inferred. Our data show critical results concerning the high temperature stability of Type IA gratings, as they undergo a drastic initial decay at 100°C, with a consequent mean index change that is severely reduced at this temperature However, the modulated index change of IA gratings remains stable at lower annealing temperatures of 80°C, and the mean index change decays at a comparable rate to Type I gratings at 80°C. Extending this work to include the thermal decay of Type IA gratings inscribed under strain shows that the application of strain quite dramatically transforms the temperature characteristics of the Type IA grating, modifying the temperature coefficient and annealing curves, with the grating showing a remarkable improvement in high temperature stability, leading to a robust grating that can survive temperatures exceeding 180°C. Under conditions of inscription under strain it is found that the temperature coefficient increases, but is maintained at a value considerably different to the Type I grating. Therefore, the combination of Type I and IA (strained) gratings make it possible to decouple temperature and strain over larger temperature excursions.

Molecular dynamics simulation of brittle fracture in silicon

The fracture process involves converting potential energy from a strained body into surface energy, thermal energy, and the energy needed to create lattice defects. In dynamic fracture, energy is also initially converted into kinetic energy. This paper uses molecular dynamics (MD) to simulate brittle frcture in silicon and determine how energy is converted from potential energy (strain energy) into other forms.

Medical students' personal experience of high-stakes failure:case studies using interpretative phenomenological analysis

Abstract (provisional): Background Failing a high-stakes assessment at medical school is a major event for those who go through the experience. Students who fail at medical school may be more likely to struggle in professional practice, therefore helping individuals overcome problems and respond appropriately is important. There is little understanding about what factors influence how individuals experience failure or make sense of the failing experience in remediation. The aim of this study was to investigate the complexity surrounding the failure experience from the student’s perspective using interpretative phenomenological analysis (IPA). Methods The accounts of 3 medical students who had failed final re-sit exams, were subjected to in-depth analysis using IPA methodology. IPA was used to analyse each transcript case-by-case allowing the researcher to make sense of the participant’s subjective world. The analysis process allowed the complexity surrounding the failure to be highlighted, alongside a narrative describing how students made sense of the experience. Results The circumstances surrounding students as they approached assessment and experienced failure at finals were a complex interaction between academic problems, personal problems (specifically finance and relationships), strained relationships with friends, family or faculty, and various mental health problems. Each student experienced multi-dimensional issues, each with their own individual combination of problems, but experienced remediation as a one-dimensional intervention with focus only on improving performance in written exams. What these students needed to be included was help with clinical skills, plus social and emotional support. Fear of termination of the their course was a barrier to open communication with staff. Conclusions These students’ experience of failure was complex. The experience of remediation is influenced by the way in which students make sense of failing. Generic remediation programmes may fail to meet the needs of students for whom personal, social and mental health issues are a part of the picture.

Reactions of singlet oxygen and singlet oxygen mimics with dicyclopropylethylenes: Comparison of reactivity and mechanisms

An extensive study of the reaction pathways of 1,1-dicyclopropyl ethylene, cis- and trans- 1,2-dicyclopropylethylenes has been undertaken with different electrophiles 4-methyl-1,2,4-triazoline-3,5-dione (MTAD), tetracyanoethylene (TCNE), and singlet oxygen $\rm(\sp1O\sb2).$ Comparison of reactivity and reaction mechanisms among the electrophiles is investigated. Singlet oxygen exhibits significantly lower reactivity compared to the other electrophiles. MTAD and TCNE react with dicyclopropylethylenes to produce predominantly $\sp{\prime\prime}2+2\sp{\prime\prime}$ adducts and a small amount of the "ene" adducts. The $\sp{\prime\prime}2+2\sp{\prime\prime}$ is the major product presumably because of the high activation energy leading to the highly strained "ene" products. Solvent trapping studies provide strong evidence of a "stepwise" mechanism, involving a zwitterionic or aziridinium imide as an intermediate from the study of the reactions products of dicyclopropylethylenes and MTAD. ^

Reactions of singlet oxygen and singlet oxygen mimics with dicyclopropylethylenes: comparison of reactivity and mechanisms

An extensive study of the reaction pathways of 1,1- dicyclopropyl ethylene, cis- and trans- 1,2-dicyclopropylethylenes has been undertaken with different electrophiles 4-methyl-1,2,4- triazoline-3,5-dione (MTAD), tetracyanoethylene (TCNE), and singlet oxygen (102). Comparison of reactivity and reaction mechanisms among the electrophiles is investigated. Singlet oxygen exhibits significantly lower reactivity compared to the other electrophiles. MTAD and TCNE react with dicyclopropylethylenes to produce predominantly "2+2" adducts and a small amount of the "ene" adducts. The "2+2" is the major product presumably because of the high activation energy leading to the highly strained "ene" products. Solvent trapping studies provide strong evidence of a "stepwise" mechanism, involving a zwitterionic or aziridinium imide as an intermediate from the study of the reactions products of dicyclopropylethylenes and MTAD.

Implementation of X-ray diffraction in the measurement of residual thermal strains

Microelectronic systems are multi-material, multi-layer structures, fabricated and exposed to environmental stresses over a wide range of temperatures. Thermal and residual stresses created by thermal mismatches in films and interconnections are a major cause of failure in microelectronic devices. Due to new device materials, increasing die size and the introduction of new materials for enhanced thermal management, differences in thermal expansions of various packaging materials have become exceedingly important and can no longer be neglected. X-ray diffraction is an analytical method using a monochromatic characteristic X-ray beam to characterize the crystal structure of various materials, by measuring the distances between planes in atomic crystalline lattice structures. As a material is strained, this interplanar spacing is correspondingly altered, and this microscopic strain is used to determine the macroscopic strain. This thesis investigates and describes the theory and implementation of X-ray diffraction in the measurement of residual thermal strains. The design of a computer controlled stress attachment stage fully compatible with an Anton Paar heat stage will be detailed. The stress determined by the diffraction method will be compared with bimetallic strip theory and finite element models.

Realism and national identity in 'Y Tu Mamá También': an audience perspective

When referring to cinema and its emancipatory potential, realism, like Plato’s pharmakon, has signified both illness and cure, poison and medicine. On the one hand, realism is regarded as the main feature of so-called classical cinema, inherently conservative and thoroughly ideological, its main raison d’être being to reify and make a particular version of the status quo believable and to pass it out as ‘reality’ (Burch, 1990; MacCabe, 1974). On the other, realism has also been interpreted as a quest for truth and social justice, as in the positivist ethos that informs documentary (Zavattini, 1953). Even in the latter sense, however, the extent to which realism has served colonizing ends when used to investigate the ‘truth’ of the Other has also been noted, rendering the form profoundly suspicious (Chow, 2007, p. 150). For realism has been a Western form of representation, one that can be traced back to the invention of perspective in painting and that peaked with the secular worldview brought about by the Enlightenment. And like realism, the nation state too is a product of the Enlightenment, nationalism being, as it were, a secular replacement for the religious - that is enchanted or fantastic - worldview. In this way, realism, cinema and nation are inextricably linked, and equally strained under the current decline of the Enlightenment paradigm. This chapter looks at Y tu Mamá También by Alfonso Cuarón (2001), a highly successful road movie with documentary features, to explore the ways in which realism, cinema and nation interact with each other in the present conditions of ‘globalization’ as experienced in Mexico. The chapter compares and contrasts various interpretations of the role of realism in this film put forward by critics and scholars and other discourses about it circulating in the media with actual ways of audience engagement with it.

Mobile Clinics & Bundled Healthcare: An Exploration of Patient Perceptions of the SughaVazhvu Approach to Chronic Care Management

As the burden of non-communicable diseases increases worldwide, it is imperative that health systems adopt delivery approaches that will enable them to provide accessible, high-quality, and low-cost care to patients that need consistent management of their lifelong conditions. This is especially true in low- and middle-income country settings, such as India, where the disease burden is high and the health sector resources to address it are limited. The subscription-based, managed care model that SughaVazhvu Healthcare—a non-profit social enterprise operating in rural Thanjavur, Tamil Nadu—has deployed demonstrates potential for ensuring continuity of care among chronic care patients in resource-strained areas. However, its effectiveness and sustainability will depend on its ability to positively impact patient health status and patient satisfaction with the care management they are receiving. Therefore, this study is not only a program appraisal to aid operational quality improvement of the SughaVazhvu Healthcare model, but also an attempt to identify the factors that affect patient satisfaction among individuals with chronic conditions actively availing services.

Experimental analysis of novel telecom source materials and devices

Incumbent telecommunication lasers emitting at 1.5 µm are fabricated on InP substrates and consist of multiple strained quantum well layers of the ternary alloy InGaAs, with barriers of InGaAsP or InGaAlAs. These lasers have been seen to exhibit very strong temperature dependence of the threshold current. This strong temperature dependence leads to a situation where external cooling equipment is required to stabilise the optical output power of these lasers. This results in a significant increase in the energy bill associated with telecommunications, as well as a large increase in equipment budgets. If the exponential growth trend of end user bandwidth demand associated with the internet continues, these inefficient lasers could see the telecommunications industry become the dominant consumer of world energy. For this reason there is strong interest in developing new, much more efficient telecommunication lasers. One avenue being investigated is the development of quantum dot lasers on InP. The confinement experienced in these low dimensional structures leads to a strong perturbation of the density of states at the band edge, and has been predicted to result in reduced temperature dependence of the threshold current in these devices. The growth of these structures is difficult due to the large lattice mismatch between InP and InAs; however, recently quantum dots elongated in one dimension, known as quantum dashes, have been demonstrated. Chapter 4 of this thesis provides an experimental analysis of one of these quantum dash lasers emitting at 1.5 µm along with a numerical investigation of threshold dynamics present in this device. Another avenue being explored to increase the efficiency of telecommunications lasers is bandstructure engineering of GaAs-based materials to emit at 1.5 µm. The cause of the strong temperature sensitivity in InP-based quantum well structures has been shown to be CHSH Auger recombination. Calculations have shown and experiments have verified that the addition of bismuth to GaAs strongly reduces the bandgap and increases the spin orbit splitting energy of the alloy GaAs1−xBix. This leads to a bandstructure condition at x = 10 % where not only is 1.5 µm emission achieved on GaAs-based material, but also the bandstructure of the material can naturally suppress the costly CHSH Auger recombination which plagues InP-based quantum-well-based material. It has been predicted that telecommunications lasers based on this material system should operate in the absence of external cooling equipment and offer electrical and optical benefits over the incumbent lasers. Chapters 5, 6, and 7 provide a first analysis of several aspects of this material system relevant to the development of high bismuth content telecommunication lasers.

The origin of incipient ferroelectricity in lead telluride.

The interactions between electrons and lattice vibrations are fundamental to materials behaviour. In the case of group IV-VI, V and related materials, these interactions are strong, and the materials exist near electronic and structural phase transitions. The prototypical example is PbTe whose incipient ferroelectric behaviour has been recently associated with large phonon anharmonicity and thermoelectricity. Here we show that it is primarily electron-phonon coupling involving electron states near the band edges that leads to the ferroelectric instability in PbTe. Using a combination of nonequilibrium lattice dynamics measurements and first principles calculations, we find that photoexcitation reduces the Peierls-like electronic instability and reinforces the paraelectric state. This weakens the long-range forces along the cubic direction tied to resonant bonding and low lattice thermal conductivity. Our results demonstrate how free-electron-laser-based ultrafast X-ray scattering can be utilized to shed light on the microscopic mechanisms that determine materials properties.

Heterogeneously grown tunable group-IV laser on silicon

Tunable tensile-strained germanium (epsilon-Ge) thin films on GaAs and heterogeneously integrated on silicon (Si) have been demonstrated using graded III-V buffer architectures grown by molecular beam epitaxy (MBE). epsilon-Ge epilayers with tunable strain from 0% to 1.95% on GaAs and 0% to 1.11% on Si were realized utilizing MBE. The detailed structural, morphological, band alignment and optical properties of these highly tensile-strained Ge materials were characterized to establish a pathway for wavelength-tunable laser emission from 1.55 μm to 2.1 μm. High-resolution X-ray analysis confirmed pseudomorphic epsilon-Ge epitaxy in which the amount of strain varied linearly as a function of indium alloy composition in the InxGa1-xAs buffer. Cross-sectional transmission electron microscopic analysis demonstrated a sharp heterointerface between the epsilon-Ge and the InxGa1-xAs layer and confirmed the strain state of the epsilon-Ge epilayer. Lowtemperature micro-photoluminescence measurements confirmed both direct and indirect bandgap radiative recombination between the Γ and L valleys of Ge to the light-hole valence band, with L-lh bandgaps of 0.68 eV and 0.65 eV demonstrated for the 0.82% and 1.11% epsilon-Ge on Si, respectively. The highly epsilon-Ge exhibited a direct bandgap, and wavelength-tunable emission was observed for all samples on both GaAs and Si. Successful heterogeneous integration of tunable epsilon-Ge quantum wells on Si paves the way for the implementation of monolithic heterogeneous devices on Si.

Rethinking Professional Practice: The Logic of Competition and the Crisis of Identity in Housing Practice

The relationship between professionalism, education and housing practice has become increasingly strained following the introduction of austerity measures and welfare reforms across a range of countries. Focusing on the development of UK housing practice, this article considers how notions of professionalism are being reshaped within the context of welfare retrenchment and how emerging tensions have both affected the identity of housing professionals and impacted on the delivery of training and education programmes. The article analyses the changing knowledges and skills valued in contemporary housing practice and considers how the sector has responded to the challenges of austerity. The central argument is that a dominant logic of competition has culminated in a crisis of identity for the sector. Although the focus of the article is on UK housing practice, the processes identified have a wider relevance for the analysis of housing and welfare delivery in developed economies.

Preparation of Polymer Nanoparticles by Ring Opening Metathesis Polymerization in Aqueous Dispersed Systems with Water-Soluble Ruthenium-based Catalyst

Ring opening metathesis polymerization (ROMP) is a variant of olefin metathesis used to polymerize strained cyclic olefins. Ruthenium-based Grubbs’ catalysts are widely used in ROMP to produce industrially important products. While highly efficient in organic solvents such as dichloromethane and toluene, these hydrophobic catalysts are not typically applied in aqueous systems. With the advancements in emulsion and miniemulsion polymerization, it is promising to conduct ROMP in an aqueous dispersed phase to generate well-defined latex nanoparticles while improving heat transfer and reducing the use of volatile organic solvents (VOCs). Herein I report the efforts made using a PEGylated ruthenium alkylidene as the catalyst to initiate ROMP in an oil-in-water miniemulsion. 1H NMR revealed that the synthesized PEGylated catalyst was stable and reactive in water. Using 1,5-cyclooctadiene (COD) as monomer, we showed the highly efficient catalyst yielded colloidally stable polymer latexes with ~ 100% conversion at room temperature. Kinetic studies demonstrated first-order kinetics with good livingness as confirmed by the shift of gel permeation chromatography (GPC) traces. Depending on the surfactants used, the particle sizes ranged from 100 to 300 nm with monomodal distributions. The more strained cyclic olefin norbornene (NB) could also be efficiently polymerized with a PEGylated ruthenium alkylidene in miniemulsion to full conversion and with minimal coagulum formation.

Education and Self-Cultivation: Foundational Changes for Existential Flourishing

The strained relationship between pedagogy and self-cultivation is often overlooked in favour of more pressing and profitable concerns within educational institutions. However, the end of education is not a well-paying job. It is often thought that education will produce a certain type of learned individual. Students are entered into educational institutions from a very young age and spend most of their youth within them, subsequently forming a part of themselves, their self-identify and agency, through these institutions. A significant amount of trust is placed in the hands of educators not only to impart information about various subject matters but to teach students how to think. This, however, is a difficult task which cannot be completely accomplished; thinking is a skill which an educator can promote but only the individual can cultivate. If self-cultivation is not the end of pedagogical practice and education, there is something deeply contradictory between the theoretical and practical values and aims of educational institutions.This thesis will address the problems caused by the neglect of self-cultivation within the pedagogical practices of contemporary educational institutions. I argue that self-cultivation, existential learning and flourishing should be the focus of these institutions. Educational institutions can make alternative efforts not only to improve the learning environment for these students but to prepare them to cope with existential questions. By acknowledging and focusing on the significance of self-cultivation, educational institutions can and should make efforts not only to teach useful, marketable skills and information but to also nurture the agency and mental well-being of the student him- or herself. My hope is that this thesis will be the first step towards answering a larger concern: How can educational institutions alleviate the struggles of students, particularly the seemingly growing number who are suffering from depression, by appealing to notions of self-cultivation?