Transient Optical Characterisation of Donor-Acceptor Block Copolymers for Use in Solar Cells

This thesis presents a study of photo-active, semiconducting block copolymers for use in molecular solar cells. Current state-of-the-art organic devices utilise blends of two (or more) materials that are co-deposited from a common solution; the resulting structures formed are determined by material properties and deposition conditions, but often result in configurations that are detrimental to device performance. An answer to this problem comes in the form of the block copolymer; using these materials, devices can be formed from a single material active layer. In addition, the counterbalance of forces within films of block copolymer can lead to nano-scale self-assembly that allows for a strong degree of control over layer equilibrium morphology. Such control will be an important step forward in the evolution of molecular solar cells. The main body of this work is concerned with the study of the photo-physics of photo-conductive block copolymers, especially the generation of free charge. First, an investigation is made into the inherent structure-function relationship in block copolymers. A varying chain length is seen to drastically affect the photoluminescence quenching and yield of long-lived charges. Photovoltaic devices made using these materials show a peak efficiency of 0.11% and correlate with the spectroscopic results, subject to a trade off between charge generation and transport/collection. In a second investigation, the effects of post-fabrication annealing on block copolymer films are considered; studies on annealed samples lead to the conclusion that domain crystallinity is a significant factor in determining the yields of long-lived charge carriers. It is found that these yields are comparable with those of a standard blend (that achieve 75% photon to electron conversion efficiency). Annealing leads to increases in photovoltaic device performance over unannealed samples, although additional control over active layer morphology is necessary for these materials to attain their potential. Following this, a comparative study is made between a block copolymer and a similarly composed blend formed from well studied polyfluorene copolymers. Further advantages of block copolymers are highlighted, including the stability of morphologies generated under different deposition conditions. Finally, a novel tool set is introduced using a block copolymer sample to emphasise the experiments potential with regard to studying interfacial photophysical effects

Testing the universality of star formation - I. Multiplicity in nearby star-forming regions

We have collated multiplicity data for five clusters (Taurus, Chamaeleon I, Ophiuchus, IC 348 and the Orion Nebula Cluster). We have applied the same mass ratio (flux ratios of ΔK≤ 2.5) and primary mass cuts (∼0.1-3.0 M⊙) to each cluster and therefore have directly comparable binary statistics for all five clusters in the separation range 62-620 au, and for Taurus, Chamaeleon I and Ophiuchus in the range 18-830 au. We find that the trend of decreasing binary fraction with cluster density is solely due to the high binary fraction of Taurus; the other clusters show no obvious trend over a factor of nearly 20 in density. With N-body simulations, we attempt to find a set of initial conditions that are able to reproduce the density, morphology and binary fractions of all five clusters. Only an initially clumpy (fractal) distribution with an initial total binary fraction of 73 per cent (17 per cent in the range 62-620 au) is able to reproduce all of the observations (albeit not very satisfactorily). Therefore, if star formation is universal, then the initial conditions must be clumpy and with a high (but not 100 per cent) binary fraction. This could suggest that most stars, including M dwarfs, form in binarie

Automatic Abstraction for Congruences

One approach to verifying bit-twiddling algorithms is to derive invariants between the bits that constitute the variables of a program. Such invariants can often be described with systems of congruences where in each equation $\vec{c} \cdot \vec{x} = d \mod m$, (unknown variable m)$is a power of two,$\vec{c}$is a vector of integer coefficients, and$\vec{x}$ is a vector of propositional variables (bits). Because of the low-level nature of these invariants and the large number of bits that are involved, it is important that the transfer functions can be derived automatically. We address this problem, showing how an analysis for bit-level congruence relationships can be decoupled into two parts: (1) a SAT-based abstraction (compilation) step which can be automated, and (2) an interpretation step that requires no SAT-solving. We exploit triangular matrix forms to derive transfer functions efficiently, even in the presence of large numbers of bits. Finally we propose program transformations that improve the analysis results

A comprehensive strategy to detect the fraudulent adulteration of herbs: The oregano approach

AbstractFraud in the global food supply chain is becoming increasingly common due to the huge profits associated with this type of criminal activity. Food commodities and ingredients that are expensive and are part of complex supply chains are particularly vulnerable. Both herbs and spices fit these criteria perfectly and yet strategies to detect fraudulent adulteration are still far from robust. An FT-IR screening method coupled to data analysis using chemometrics and a second method using LC-HRMS were developed, with the latter detecting commonly used adulterants by biomarker identification. The two tier testing strategy was applied to 78 samples obtained from a variety of retail and on-line sources. There was 100% agreement between the two tests that over 24% of all samples tested had some form of adulterants present. The innovative strategy devised could potentially be used for testing the global supply chains for fraud in many different forms of herbs

High-Resolution Spectroscopy of the Planetary Host HD 13189: Highly-Evolved and Metal-Poor

We report on the abundances of 13 elements in the planetary host HD 13189, a massive giant star. Abundances are found to be sub-solar, with [Fe/H] = -0.58 +/- 0.04$; HD 13189 is one of the most metal-poor planetary hosts yet discovered. Abundance ratios relative to Fe show no peculiarities with respect to random field stars. A census of metallicities of the seven currently known planet-harboring giants results in a distribution that is more metal-poor than the well-known metal-rich distribution of main sequence (MS) planetary hosts. This finding is discussed in terms of accretion of H-depleted material, one of the possible mechanisms responsible for the high-metallicity distribution of MS stars with planets. We estimate the mass of the HD 13189 progenitor to be 3.5 M_sun but cannot constrain this value to better than 2-6 M_sun. A stellar mass of 3.5 M_sun implies a planetary mass of m sin i = 14.0 +/- 0.8 M_J, placing the companion at the planet/brown dwarf boundary. Given its physical characteristics, the HD 13189 system is potentially unique among planetary systems, and its continued investigation should provide invaluable data to extrasolar planetary research.Comment: 14 pages, 2 figures; Accepted for publication in ApJ Letter

The removal of shear-ellipticity correlations from the cosmic shear signal: Influence of photometric redshift errors on the nulling technique

Cosmic shear is regarded one of the most powerful probes to reveal the properties of dark matter and dark energy. To fully utilize its potential, one has to be able to control systematic effects down to below the level of the statistical parameter errors. Particularly worrisome in this respect is intrinsic alignment, causing considerable parameter biases via correlations between the intrinsic ellipticities of galaxies and the gravitational shear, which mimic lensing. In an earlier work we have proposed a nulling technique that downweights this systematic, only making use of its well-known redshift dependence. We assess the practicability of nulling, given realistic conditions on photometric redshift information. For several simplified intrinsic alignment models and a wide range of photometric redshift characteristics we calculate an average bias before and after nulling. Modifications of the technique are introduced to optimize the bias removal and minimize the information loss by nulling. We demonstrate that one of the presented versions is close to optimal in terms of bias removal, given high quality of photometric redshifts. For excellent photometric redshift information, i.e. at least 10 bins with a small dispersion, a negligible fraction of catastrophic outliers, and precise knowledge about the redshift distributions, one version of nulling is capable of reducing the shear-intrinsic ellipticity contamination by at least a factor of 100. Alternatively, we describe a robust nulling variant which suppresses the systematic signal by about 10 for a very broad range of photometric redshift configurations. Irrespective of the photometric redshift quality, a loss of statistical power is inherent to nulling, which amounts to a decrease of the order 50% in terms of our figure of merit.Comment: 26 pages, including 16 figures; minor changes to match accepted version; published in Astronomy and Astrophysic

The Effect of Authigenic Clays on Fault Zone Permeability

Leverhulme Trust (GrantNumber(s): ECF-2020-560) Natural Environment Research Council (GrantNumber(s): NE/N003063/1) Open access via Wiley agreementPeer reviewedPublisher PD