Polythiophene nanofibres for optoelectronic applications

This thesis reports on the fabrication and characterisation of self-assembled nanofibres of poly(3-hexylthiophene) (P3HT), and demonstrates how these nanofibres can be used in applications like thin-film transistors and solar cells. The first results chapter describes a preparation method of P3HT nanofibres in a solution of chlorobenzene by using di-tert butyl peroxide (DTBP) as an additive. This method allows the fabrication of films of P3HT with high molecular order and gives control over the film retention. The films are characterised using a range of experimental techniques, including optical absorption, X-ray diffraction and atomic force microscopy, which also allows to determine the dimensions of individual, separated nanofibres. A more detailed investigation into the temperature dependence of the photoluminescence (PL) of nanofibre films in comparison to P3HT thin-films is presented in the second results chapter. The line-shape of the measured PL of the nanofibres shows significant differences to the thin-film, which is most distinctive at a temperature of around 150K. At this temperature, the measurements show a change of the emission characteristics for the nanofibres which is absent in the thin-film. The cause for the observed transition can be related to the increased planarisation of the polymer backbone inside the nanofibres with increasing temperature. This gives rise to more dominant intrachain coupling for the fibres, in contrast to predominantly interchain coupling in P3HT thin-films. The third results chapter demonstrates the application of the nanofibre films in thin-film transistors and solar cells. It is shown how the high molecular order of the nanofibres in combination with the formation of fibre networks can be used to control the field-effect mobility of P3HT films. Solar cells are fabricated by successive deposition of a nanofibre film and an electron acceptor layer, resulting in power conversion efficiencies comparable to bulk heterojunction solar cells

Toxicty of a Serotonin-derived Neuromelanin

Neuroscience - Vision and Functional Brain Imaging Poster SessionIntroduction: POCD (Postoperative Cognitive Dysfunction) is associated with increased mortality and disability and may develop as a consequence of lipid peroxidative byproducts (i.e. acrolein), which accumulate with aging. We previously showed that sevoflurane sequesters acrolein, which promotes the formation of a novel species of neuromelanin (NM) that may play a role in POCD. In this current study, we examined the properties of NM and hypothesized that this novel serotonin-derived melanoid (SDM) product may be neurotoxic. Methods: SDM was produced at the interface of an upper aqueous phase containing serotonin and a lower sevoflurane phase containing acrolein. Uni-lamellar vesicles (ULVs) of dioleoyl-phosphatidylcholine were made using an extrusion technique. The interaction of SDM with ULVs was examined using two lipid membrane probes: diphenyl-hexatriene (DPH) and merocyanine (MC). Vesicle disruption was investigated by monitoring the leakage of dye from calcein-loaded ULVs. Absorbance spectra of SDM were also examined. Statistical analysis involved linear regression and unpaired Student t-tests (p<0.05). Results: We observed that SDM decreased DPH fluorescence anisotropy and increased the temperature-dependent change in anisotropy of DPH. SDM increased the ratio of absorbance (570nm/530nm) of MC-bound ULVs. Using calcein-loaded ULVs, SDM increased detergent-mediated calcein leakage. The intense absorbance band below 250nm of SDM was dramatically altered in the presence of ULVs, yielding three well-resolved peaks from a single broad band. Conclusion: From these data we conclude that SDM has the potential of being neurotoxic. Discussion: This study further characterizes SDM as an important species of NM. SDM disorganized the acyl chains and the phospholipid head groups of ULVs. The electronic structure of SDM was dramatically altered upon interaction with ULVs. We also observed that SDM enhanced detergent-mediated leakage of loaded ULVs, suggesting that SDM may be neurotoxic. We propose that inhalational agents that sequester acrolein [3], may promote the production of certain species of NM that deplete local serotonin and enhance neuronal vulnerability

Enhanced crystallinity and film retention of P3HT thin-films for efficient organic solar cells by use of preformed nanofibers in solution

We report the preparation of films of poly(3-hexylthiophene) nanofibers suitable for fabrication of efficient multilayer solar cells by successive deposition of donor and acceptor layers from the same solvent. The nanofibers are obtained by addition of di-tert-butyl peroxide (DTBP) to a solution of P3HT in chlorobenzene. Interestingly, by varying the concentration of DTBP we are able to control both crystallinity and film retention of the spin-cast films. We also investigate the influence of the DTBP-induced crystallization on charge transport by thin-film transistor measurements, and find a more than five-fold increase in the hole mobility of nanofiber films compared to pure P3HT. We attribute this effect to the synergistic effects of increased crystallinity of the fibers and the formation of micrometer-sized fiber networks. We further demonstrate how it is possible to make use of the high film retention to fabricate photovoltaic devices by subsequent deposition of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) from a chlorobenzene solution on top of the nanofiber film. The presence of a relatively large crystalline phase strongly affects the diffusion behavior of PCBM into the P3HT film, resulting in a morphology which is different from that of common bulk heterojunction solar cells and resembles a bilayer structure, as can be inferred from comparison of the external quantum efficiency spectra. However, a high power conversion efficiency of 2.3% suggests that there is still a significant intermixing of the two materials taking place

How analysts think: sense-making strategies in the analysis of temporal evolution and criminal network structures and activities

Analysis of criminal activity based on offenders’ social networks is an established procedure in intelligence analysis. The complexity of the data poses an obstacle for analysts to gauge network developments, e.g. detect emerging problems. Visualization is a powerful tool to achieve this, but it is essential to know how the analysts’ sense-making strategies can be supported most efficiently. Based on a think aloud study we identified ten cognitive strategies on a general level to be useful for designers. We also provide some examples how these strategies can be supported through appropriate visualizations

Sense-making strategies in explorative intelligence analysis of network evolutions

Visualising how social networks evolve is important in intelligence analysis in order to detect and monitor issues, such as emerging crime patterns or rapidly growing groups of offenders. It remains an open research question how this type of information should be presented for visual exploration. To get a sense of how users work with different types of visualisations, we evaluate a matrix and a node-link diagram in a controlled thinking aloud study. We describe the sense-making strategies that users adopted during explorative and realistic tasks. Thereby, we focus on the user behaviour in switching between the two visualisations and propose a set of nine strategies. Based on a qualitative and quantitative content analysis we show which visualisation supports which strategy better. We find that the two visualisations clearly support intelligence tasks and that for some tasks the combined use is more advantageous than the use of an individual visualisation

Two-Tone Optomechanical Instability and Its Fundamental Implications for Backaction-Evading Measurements

While quantum mechanics imposes a fundamental limit on the precision of interferometric measurements of mechanical motion due to measurement backaction, the nonlinear nature of the coupling also leads to parametric instabilities that place practical limits on the sensitivity by limiting the power in the interferometer. Such instabilities have been extensively studied in the context of gravitational wave detectors, and their presence has recently been reported in Advanced LIGO. Here, we observe experimentally and describe theoretically a new type of optomechanical instability that arises in two-tone backaction-evading (BAE) measurements, designed to overcome the standard quantum limit, and demonstrate the effect in the optical domain with a photonic crystal nanobeam, and in the microwave domain with a micromechanical oscillator coupled to a microwave resonator. In contrast to the well-known oscillatory parametric instability that occurs in single-tone, blue-detuned pumping, which is characterized by a vanishing effective mechanical damping, the parametric instability in balanced two-tone optomechanics is exponential, and is a result of small detuning errors in the two pump frequencies. Its origin can be understood in a rotating frame as the vanishing of the effective mechanical frequency due to an optical spring effect. Counterintuitively, the instability occurs even in the presence of perfectly balanced intracavity fields, and can occur for both signs of detuning. We find excellent quantitative agreement with our theoretical predictions. Since the constraints on tuning accuracy become stricter with increasing probe power, it imposes a fundamental limitation on BAE measurements, as well as other two-tone schemes. In addition to introducing a new limitation in two-tone BAE measurements, the results also introduce a new type of nonlinear dynamics in cavity optomechanics

The shape of equality: discourses around the Section 28 repeal in Scotland

This article focuses on conceptualizations of equality in the discourses deployed in the campaign to repeal Section 28 in Scotland. I use the parliamentary debates and two newspapers: the Daily Record, which supported the campaign to Keep the Clause, and The Guardian, which supported repeal, to exemplify the different discursive articulations around equality and citizenship. I suggest that the Scottish example provides further evidence of the ways in which liberalism naturalizes heterosexuality as the standard for citizenship and thus bequeaths a hierarchy of 'equality' and citizenship in the realm of sexuality, wherein lesbian and gay citizenship is either rendered invalid or characterized as 'special rights'. However, within the narrow confines of the parliamentary debates, more expansive and differentiated notions of citizenship and equality are evident. Whilst I conclude that the 'shape' of equality achieved through the repeal has been moulded to support institutionalized heterosexuality - with Section 28 replaced by statutory guidelines on sex education which advocate marriage - I also suggest equality is contested, both through the recognition of transformations in heterosexual family forms and the appeal to non-discrimination as a democratic principle. It is possible, therefore, that current destabilizations of the heterosexual social order simultaneously destabilize the precepts of liberal democracy

A New Normal: Integrating Lived Experience Into Scientific Data Syntheses

status: publishe