Metal window electrodes for organic photovoltaics

The work presented in this thesis focuses on the development ultra-thin metal film electrodes for organic photovoltaics (OPVs) with the aim of boosting device performance, lowering the cost and/or extending the range potential application. Chapter 1 gives a general overview of OPVs, including the materials used for their fabrication and the fundamental processes underpinning OPV’s operation. The experimental techniques and equipment used are described in Chapter 2. Chapter 3 describes the development of a solvent free method for the fabrication of highly transparent ultra-thin Au films on glass based on co-deposition of a mixed molecular adhesive layer prior to Au thermal evaporation. By integrating microsphere lithography into the fabrication process the transparency could be improved via the incorporation of a random array of micron-sized circular apertures into the film. In Chapter 4 it is shown that these films are amenable to rapid thermal annealing to realise highly crystalline window electrodes with improved transparency and conductivity. By capping these films with a very thin transition metal oxide layer their thermal stability can be dramatically improved, whilst at the same time improving their far field transparency. In Chapter 5 the molecular adhesive method for the fabrication of ultra-thin Au films on glass is translated to the technologically important flexible substrates and extended to the lower cost coinage metals Ag and Cu. In Chapter 6 a lithography-free approach to fabricating thin Au and Ag films with a dense array of sub-wavelength apertures is reported. These electrodes support surface plasmon resonances which couple strongly with visible light concentrating it near to the electrode surface, thereby increasing light harvesting. Chapter 7 shows how the electrodes developed in Chapter 3 can be used to investigate a fundamental question of importance in OPV research and indicates the direction of future work. The results of chapters 3, 5 and 6 have been published in peer reviewed scientific journals

Widely applicable coinage metal window electrodes on flexible polyester substrates applied to organic photovoltaics

The fabrication, exceptional properties, and application of 8 nm thick Cu, Ag, Au, and Cu/Ag bilayer electrodes on flexible polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) substrates is reported. These electrodes are fabricated using a solvent free process in which the plastic surface is chemically modified with a molecular monolayer of thiol and amine terminated alkylsilanes prior to metal deposition. The resulting electrodes have a sheet resistance of ≤14 Ω sq–1, are exceptionally robust and can be rapidly thermally annealed at 200 °C to reduce their sheet resistance to ≤9 Ω sq–1. Notably, annealing Au electrodes briefly at 200 °C causes the surface to revert almost entirely to the {111} face, rendering it ideal as a model electrode for fundamental science and practical application alike. The power conversion efficiency of 1 cm2 organic photovoltaics (OPVs) employing 8 nm Ag and Au films as the hole-extracting window electrode exhibit performance comparable to those on indium–tin oxide, with the advantage that they are resistant to repeated bending through a small radius of curvature and are chemically well-defined. OPVs employing Cu and bilayer Cu:Ag electrodes exhibit inferior performance due to a lower open-circuit voltage and fill factor. Measurements of the interfacial energetics made using the Kelvin probe technique provide insight into the physical reason for this difference. The results show how coinage metal electrodes offer a viable alternative to ITO on flexible substrates for OPVs and highlight the challenges associated with the use of Cu as an electrode material in this contex

Training for the Bar - Educational (R)evolution

On 25th June 2013, the Legal Education and Training Review published its report on the legal education landscape and made 26 recommendations for change. Over the past 5 years the legal regulators have considered these recommendations and developed and consulted on new education and training pathways and assessment strategies. This article focusses on the Bar Standards Board’s Future Bar Training Programme and provides commentary, explanation and a rationale for training for the Bar from 2020

Bilirubin Nanoparticles Reduce Diet-Induced Hepatic Steatosis, Improve Fat Utilization, and Increase Plasma β-Hydroxybutyrate

The inverse relationship of plasma bilirubin levels with liver fat accumulation has prompted the possibility of bilirubin as a therapeutic for non-alcoholic fatty liver disease. Here, we used diet-induced obese mice with non-alcoholic fatty liver disease treated with pegylated bilirubin (bilirubin nanoparticles) or vehicle control to determine the impact on hepatic lipid accumulation. The bilirubin nanoparticles significantly reduced hepatic fat, triglyceride accumulation, de novo lipogenesis, and serum levels of liver dysfunction marker aspartate transaminase and ApoB100 containing very-low-density lipoprotein. The bilirubin nanoparticles improved liver function and activated the hepatic β-oxidation pathway by increasing PPARα and acyl-coenzyme A oxidase 1. The bilirubin nanoparticles also significantly elevated plasma levels of the ketone β-hydroxybutyrate and lowered liver fat accumulation. This study demonstrates that bilirubin nanoparticles induce hepatic fat utilization, raise plasma ketones, and reduce hepatic steatosis, opening new therapeutic avenues for NAFLD

Ecology explains anhydrobiotic performance across tardigrades, but the shared evolutionary history matters more

Desiccation stress is lethal to most animals. However, some microinvertebrate groups have evolved coping strategies, such as the ability to undergo anhydrobiosis (i.e. survival despite the loss of almost all body water). Tardigrades are one such group, where the molecular mechanisms of anhydrobiosis have been more thoroughly studied. Despite the ecological, evolutionary and biotechnological importance of anhydrobiosis, little is known about its inter- and intra-specific variability nor its relationship with natural habitat conditions or phylogenetic history.We developed a new index-anhydrobiotic recovery index (ARI)-to evaluate the anhydrobiotic performance of tardigrade populations from the family Macrobiotidae. Moreover, we compared the explanatory role of habitat humidity and phylogenetic history on this trait using a variance partitioning approach.We found that ARI is correlated with both microhabitat humidity and yearly rainfall, but it is mostly driven by phylogenetic niche conservatism (i.e. a high portion of ARI variation is explained by phylogeny alone). Finally, we showed that anhydrobiotic performance is highly variable, even between closely related species, and that their response to local ecological conditions is tightly linked to their phylogenetic history.This study not only presents key insights into an emerging model system, but also provides a new methodological approach for wider scale studies of the ecological and evolutionary implications of anhydrobiosis

Di-, tri- and tetra-5'-O-phosphorothioadenosyl substituted polyols as inhibitors of Fhit: Importance of the α-β bridging oxygen and β phosphorus replacement

BACKGROUND: The human FHIT gene is inactivated early in the development of many human cancers and loss of Fhit in mouse predisposes to cancer while reintroduction of FHIT suppresses tumor formation via induction of apoptosis. Fhit protein, a diadenosine polyphosphate hydrolase, does not require hydrolase activity to function in tumor suppression and may signal for apoptosis as an enzyme-substrate complex. Thus, high affinity nonhydrolyzable substrate analogs may either promote or antagonize Fhit function, depending on their features, in Fhit + cells. Previously synthesized analogs with phosphorothioadenosyl substitutions and "supercharged" branches do not bind better than natural substrates and thus have limited potential as cellular probes. RESULTS: Here we link adenosine 5'-O-phosphates and phosphorothioates to short-chain polyols to generate a series of substrate analogs. We obtain structure-activity data in the form of in vitro Fhit inhibition for four types of analog substitutions and describe two compounds, inhibitory constants for which are 65 and 75-fold lower than natural substrates. CONCLUSIONS: The best Fhit inhibitors obtained to date separate two or more 5'-O-phosphoromonothioadenosyl moieties with as many bond lengths as in AppppA, maintain oxygen at the location of the α-β bridging oxygen, and replace carbon for the β phosphorus

Evaluating ChatGPT's Decimal Skills and Feedback Generation in a Digital Learning Game

While open-ended self-explanations have been shown to promote robust learning in multiple studies, they pose significant challenges to automated grading and feedback in technology-enhanced learning, due to the unconstrained nature of the students' input. Our work investigates whether recent advances in Large Language Models, and in particular ChatGPT, can address this issue. Using decimal exercises and student data from a prior study of the learning game Decimal Point, with more than 5,000 open-ended self-explanation responses, we investigate ChatGPT's capability in (1) solving the in-game exercises, (2) determining the correctness of students' answers, and (3) providing meaningful feedback to incorrect answers. Our results showed that ChatGPT can respond well to conceptual questions, but struggled with decimal place values and number line problems. In addition, it was able to accurately assess the correctness of 75% of the students' answers and generated generally high-quality feedback, similar to human instructors. We conclude with a discussion of ChatGPT's strengths and weaknesses and suggest several venues for extending its use cases in digital teaching and learning.Comment: Be accepted as a Research Paper in 18th European Conference on Technology Enhanced Learnin

Analysis of Student Perceptions of Just-In-Time Teaching Pedagogy in PharmD Microbiology and Immunology Courses

Just-In-Time Teaching (JiTT) active learning pedagogy is utilized by various disciplines, but its value in a professional pharmacy curriculum has not yet been demonstrated. The purpose of our research study is to implement and evaluate JiTT in a Doctor of Pharmacy (PharmD) program. The impetus in implementing JiTT into a PharmD curriculum was to provide students with an out-of-classroom learning opportunity to enhance knowledge-based skills. The current study summarizes the implementation of JiTT in four distinct instances: two iterations of the required courses “Integrated Microbiology and Virology” (Fall 2016 and Fall 2017) and “Integrated Immunology” (Winter 2016–2017 and Winter 2017–2018). JiTT included knowledge-based questions in multiple-choice format, integrated case studies, and student responses prior to the actual lecture session. After the conclusion of each course, students were asked to provide feedback on the utilization of JiTT by way of an anonymous survey. Following the Fall 2016 iteration of the Microbiology & Virology course, students found the integrated case studies to be beneficial (mean = 3.27 out of a maximum of 4, SD = 0.62), and their overall endorsement of JiTT was high (mean = 3.61 out of 4, SD = 0.50). For the other three courses included in this study, the primary dependent variable was the student’s average rating of JiTT, rated on a five-point scale. Aggregating the scores from the Fall 2017 iteration of the Integrated Microbiology & Virology course and both instances of the Immunology course, students rated JiTT very favorably (mean = 4.17 out of a maximum of 5, SD = 0.77). Students’ performances in JiTT-based courses were compared against non-JiTT-based courses. Analysis of assessment data for student’s performance on knowledge-based questions showed JiTT was helpful for student learning and JiTT-based courses had more consistent exam scores compared to non-JiTT-based courses. The current results are a promising initial step in validating the usefulness of JiTT in a pharmacy program and lays the foundation for future studies aimed at a direct comparison between a traditional lecture style and JiTT pedagogy implemented into PharmD curricula