Synthesis and characterisation of interfacial layers in organic solar cells

The quest for renewable energy sources has led to growing attention in the research of organic photovoltaics (OPVs), as a promising alternative to fossil fuels, since these devices have low manufacturing costs and attractive end-user qualities, such as ease of installation and maintenance. Wide application of OPVs is majorly limited by the devices lifetime. With the development of new encapsulation materials, some degradation factors, such as water and oxygen ingress, can almost be excluded, whereas the thermal degradation of the devices remains a major issue. Two aspects have to be addressed to solve the problem of thermal instability: bulk effects in the photoactive layer and interfacial effects at the photoactive layer/charge-transporting layers. In this work, the interface between photoactive layer and electron-transporting zinc oxide (ZnO) in devices with inverted architecture was engineered by introducing polymeric interlayers, based on zinc-binding ligands, such as 3,4-dihydroxybenzene and 8-hydroxyquinoline. Also, a cross-linkable layer of poly(3,4-dimethoxystyrene) and its fullerene derivative were studied. At first, controlled reversible addition-fragmentation chain transfer (RAFT) polymerisation was employed to achieve well-defined polymers in a range of molar masses, all bearing a chain-end functionality for further modifications. Resulting polymers have been fully characterised, including their thermal and optical properties, and introduced as interlayers to study their effect on the initial device performance and thermal stability. Poly(3,4-dihydroxystyrene) and its fullerene derivative were found unsuitable for application in devices as they increased the work function of ZnO and created a barrier for electron extraction. On the other hand, their parental polymer, poly(3,4-dimethoxystyrene), and its fullerene derivative, upon cross-linking, resulted in enhanced efficiency and stability of devices, if compared to control. Polymers based on 8-hydroxyquinoline ligand had a negative effect on the initial stability of the devices, but increased the lifetime of the cells under accelerated thermal stress. Comprehensive studies of the key mechanisms, determining efficiency, such as charge generation and extraction, were performed by using time-resolved electrical and spectroscopic techniques, in order to understand in detail the effect of the interlayers on the device performance. Obtained results allow deeper insight into mechanisms of degradation that limit the lifetime of devices and prompt the design of better materials for the interface stabilisation.

Identification of the degradation mechanisms of organic solar cells:active layer and interfacial layers

Organic Solar Cells (OSCs) represent a photovoltaic technology with multiple interesting application properties. However, the establishment of this technology into the market is subject to the achievement of operational lifetimes appropriate to their application purposes. Thus, comprehensive understanding of the degradation mechanisms occurring in OSCs is mandatory in both selecting more intrinsically stable components and/or device architectures and implementing strategies that mitigate the encountered stability issues. Inverted devices can suffer from mechanical stress and delamination at the interface between the active layer, e.g. poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM), and the hole transport layer, e.g. poly(3,4-ethylenedioxythiophene):poly(p-styrene sulfonate) (PEDOT:PSS). This work proposes the incorporation of a thin adhesive interlayer, consisting of a diblock copolymer composed of a P3HT block and a thermally-triggerable, alkyl-protected PSS block. In this context, the synthesis of poly(neopentyl p-styrene sulfonate) (PNSS) with controlled molar mass and low dispersity (Ð ≤ 1.50) via Reversible Addition-Fragmentation chain Transfer (RAFT) polymerisation has been extensively studied. Subsequently, Atomic Force Microscopy (AFM) was explored to characterise the thermal deprotection of P3HT-b-PNSS thin layers to yield amphiphilic P3HT-b-PSS, indicating that surface deprotection prior to thermal treatment could occur. Finally, structural variation of the alkyl protecting group in PSS allowed reducing the thermal treatment duration from 3 hours (P3HT-b-PNSS) to 45 minutes for the poly(isobutyl p-styrene sulfonate) (PiBSS) analogous copolymer. Another critical issue regarding the stability of OSCs is the sunlight-driven chemical degradation of the active layer. In the study herein, the combination of experimental techniques and theoretical calculations has allowed identification of the structural weaknesses of poly[(4,4’- bis(2-ethylhexyl) dithieno [3,2-b:2’,3’-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5’-diyl], Si-PCPDTBT, upon photochemical treatment in air. Additionally, the study of the relative photodegradation rates in air of a series of polymers with systematically modified backbones and/or alkyl side chains has shown no direct correlation between chemical structure and stability. It is proposed instead that photostability is highly dependent on the crystalline character of the deposited films. Furthermore, it was verified that photostability of blends based on these polymers is dictated by the (de)stabilising effect that [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) has over each polymer. Finally, a multiscale analysis on the degradation of solar cells based on poly[4,4' bis(2- ethylhexyl) dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-[2,5 bis(3 tetradecylthiophen 2-yl)thiazole[5,4-d]thiazole)-1,8-diyl] and PCBM, indicated that by judicious selection of device layers, architectures, and encapsulation materials, operational lifetimes up to 3.3 years with no efficiency losses can be successfully achieved.

Crack tip stress study for elastic-perfectly plastic materials with some applications

The problems of plasticity and non-linear fracture mechanics have been generally recognized as the most difficult problems of solid mechanics. The present dissertation is devoted to some problems on the intersection of both plasticity and non-linear fracture mechanics. The crack tip is responsible for the crack growth and therefore is the focus of fracture science. The problem of crack has been studied by an army of outstanding scholars and engineers in this century, but has not, as yet, been solved for many important practical situations. The aim of this investigation is to provide an analytical solution to the problem of plasticity at the crack tip for elastic-perfectly plastic materials and to apply the solution to a classical problem of the mechanics of composite materials.^ In this work, the stresses inside the plastic region near the crack tip in a composite material made of two different elastic-perfectly plastic materials are studied. The problems of an interface crack, a crack impinging an interface at the right angle and at arbitrary angles are examined. The constituent materials are assumed to obey the Huber-Mises yielding condition criterion. The theory of slip lines for plane strain is utilized. For the particular homogeneous case these problems have two solutions: the continuous solution found earlier by Prandtl and modified by Hill and Sokolovsky, and the discontinuous solution found later by Cherepanov. The same type of solutions were discovered in the inhomogeneous problems of the present study. Some reasons to prefer the discontinuous solution are provided. The method is also applied to the analysis of a contact problem and a push-in/pull-out problem to determine the critical load for plasticity in these classical problems of the mechanics of composite materials.^ The results of this dissertation published in three journal articles (two of which are under revision) will also be presented in the Invited Lecture at the 7$\rm\sp{th}$ International Conference on Plasticity (Cancun, Mexico, January 1999). ^

GIS layers of seafloor characteristics in the Azores region (North Atlantic), links to files in ArcGIS format

Inventory of some important datasets related to the physical characteristics of the seafloor surrounding the Azores Archipelago. The objective is to ensure that our compilation is readily available for any researchers interested in this type information but also to support institutions responsible for the management and conservation of local resources.

Quarternary tephra layers in sediment cores from the Bellingshausen Sea and Scotia Sea

The Southern Ocean is a region of the world's ocean which is fundamental to the generation of cold deep ocean water which drives the global therrno-haline circulation. Previous investigations of deep-sea sediments south of the Polar Front have been significantly constrained by the lack of a suitable correlation and dating technique. In this study, deep-sea sediment cores from the Bellingshausen, Scotia and Weddell seas have been investigated for the presence of tephra layers. The major oxide and trace element composition of glass shards have been used to correlate tephra isochrons over distances in excess of 600 km. The source volcanoes for individual tephra layers have been identified. Atmospheric transport distances greater than 1500 km for >32 pm shards are reported. One megascopic tephra is identified and correlated across 7 sediment drifts on the continental rise in the Bellingshausen Sea. Its occurrence in a sedimentary unit that has been biostratigraphically dated to delta 18O substage 5e identifies it as a key regional marker horizon for that stage. An unusual bimodal megascopic ash layer erupted from Deception Island, South Shetland Islands, has been correlated between 6 sediment cores which form a 600 km NE-SW transect from the central Scotia Sea to Jane Basin. This megascopic ash layer has been 14C dated at c. 10,670 years BP. It represents the last significant input of tephra into the Scotia Sea or Jane Basin from that volcano and forms an important early Holocene marker horizon for the region. Five disseminated tephras can be correlated to varying extents across the central Scotia Sea cores. Together with the megascopic tephra they form a tephrostratigraphic framework that will greatly aid palaeoclimatic, palaeoenvironrnental and palaeoceanographic investigations in the region.

Age determination of North Atlantic sediment cores

Available overwash records from coastal barrier systems document significant variability in North Atlantic hurricane activity during the late Holocene. The same climate forcings that may have controlled cyclone activity over this interval (e.g., the West African Monsoon, El Niño-Southern Oscillation (ENSO)) show abrupt changes around 6000 yrs B.P., but most coastal sedimentary records do not span this time period. Establishing longer records is essential for understanding mid-Holocene patterns of storminess and their climatic drivers, which will lead to better forecasting of how climate change over the next century may affect tropical cyclone frequency and intensity. Storms are thought to be an important mechanism for transporting coarse sediment from shallow carbonate platforms to the deep-sea, and bank-edge sediments may offer an unexplored archive of long-term hurricane activity. Here, we develop this new approach, reconstructing more than 7000 years of North Atlantic hurricane variability using coarse-grained deposits in sediment cores from the leeward margin of the Great Bahama Bank. High energy event layers within the resulting archive are (1) broadly correlated throughout an offbank transect of multi-cores, (2) closely matched with historic hurricane events, and (3) synchronous with previous intervals of heightened North Atlantic hurricane activity in overwash reconstructions from Puerto Rico and elsewhere in the Bahamas. Lower storm frequency prior to 4400 yrs B.P. in our records suggests that precession and increased NH summer insolation may have greatly limited hurricane potential intensity, outweighing weakened ENSO and a stronger West African Monsoon-factors thought to be favorable for hurricane development.

Metabolic Effects Associated with ICS in Patients with COPD and Comorbid Type 2 Diabetes : A Historical Matched Cohort Study

Funding: The analyses were funded by Boehringer Ingelheim. Access to data from the Optimum Patient Care Research Database was co-funded by Research in Real Life Ltd. The funder, Boehringer Ingelheim, had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript. Rafael Mares is employed by Research in Real Life Ltd., which provided support in the form of salary for author RM but did not have any additional role in the study design, decision to publish, or preparation of the manuscript. The specific role of this author is articulated in the ‘author contributions’ section.

Managing the multiplicities of graduate level education! Are Master’s students’ expectations matched by their experiences?

With rapid increases in student fees reflecting moves towards a QUASI Market model of Higher Education in the UK and across much of the Western World[1], many universities find themselves having to meet progressively higher levels of student expectations[2]. This is particularly the case at undergraduate level, where increases in fees over the past decade have far exceeded inflation. Yet with so much attention on ‘consumer savvy’ undergraduates, the question of whether Master’s level students’ expectations are matched by their experiences is one which remains largely unanswered. Grounded in an empirically grounded approach to learning and teaching developed by the paper authors[3], this paper sets out to being to answer this question. In doing so it makes a distinctive contribution to debates about graduate level engineering education and concludes with a number of recommendations. Discussion: The ‘MSc: Managing Expectations’ Project analyses the expectations and experiences of Graduate level Engineering Management Students over a two year period. Focusingon the ‘student experience’, three main concepts are identified as being particular relevant to enhancing learning [3]: Relationships: Variety: Synergy. Relationships: Based on empirical research, the significance of Relationships within the academic environment is discussed with particular attention being paid to the value of students’ social and academic support networks, including academic tutoring. Variety: Grounded in a statistical analysis of ‘engagement data’ together with survey and interview findings, the concept of variety critically examines students’ perspectives and experiencesof different approaches to learning and teaching. Synergy: Possibly the most important concept discussed within this paper, the need for constructively aligned curriculum is extended to reflect the students’ apriori knowledge and experienceas well as employer and societal demands and expectations. The conclusion brings the different concepts within the discussion together, providing a set of practical recommendations for colleagues working both at graduate and undergraduate level. References 1.Gibbs, P. (2001) "Higher education as a market: a problem or solution?." Studies in Higher Education 26. 1. pp. 85-94. 2.Tricker, T., (2005) Student Expectations-How do we measure up. University of Sheffield. Available from: http://www.persons.org.uk/tricker%20paper.pdf Accessed 9/10/14 3.Clark, R. & Andrews, J. (2014). Relationships, Variety & Synergy [RVS]: The Vital Ingredients for Scholarship in Engineering Education? A Case-Study. European Journal of Engineering Education. 39.6. pp. 585-600.

Pre-formulation and systematic evaluation of amino acid assisted permeability of insulin across in vitro buccal cell layers

The aim of this work was to investigate alternative safe and effective permeation enhancers for buccal peptide delivery. Basic amino acids improved insulin solubility in water while 200 and 400 µg/mL lysine significantly increased insulin solubility in HBSS. Permeability data showed a significant improvement in insulin permeation especially for 10 µg/mL of lysine (p < 0.05) and 10 µg/mL histidine (p < 0.001), 100 µg/mL of glutamic acid (p < 0.05) and 200 µg/mL of glutamic acid and aspartic acid (p < 0.001) without affecting cell integrity; in contrast to sodium deoxycholate which enhanced insulin permeability but was toxic to the cells. It was hypothesized that both amino acids and insulin were ionised at buccal cavity pH and able to form stable ion pairs which penetrated the cells as one entity; while possibly triggering amino acid nutrient transporters on cell surfaces. Evidence of these transport mechanisms was seen with reduction of insulin transport at suboptimal temperatures as well as with basal-to-apical vectoral transport, and confocal imaging of transcellular insulin transport. These results obtained for insulin is the first indication of a possible amino acid mediated transport of insulin via formation of insulin-amino acid neutral complexes by the ion pairing mechanism.

Investigation of PHY, MAC and APP layers for adaptive and cross-layer optimization in IEEE802.11 WLAN

Due to huge popularity of portable terminals based on Wireless LANs and increasing demand for multimedia services from these terminals, the earlier structures and protocols are insufficient to cover the requirements of emerging networks and communications. Most research in this field is tailored to find more efficient ways to optimize the quality of wireless LAN regarding the requirements of multimedia services. Our work is to investigate the effects of modulation modes at the physical layer, retry limits at the MAC layer and packet sizes at the application layer over the quality of media packet transmission. Interrelation among these parameters to extract a cross-layer idea will be discussed as well. We will show how these parameters from different layers jointly contribute to the performance of service delivery by the network. The results obtained could form a basis to suggest independent optimization in each layer (an adaptive approach) or optimization of a set of parameters from different layers (a cross-layer approach). Our simulation model is implemented in the NS-2 simulator. Throughput and delay (latency) of packet transmission are the quantities of our assessments. © 2010 IEEE.

Bottom-up growth of fully transparent contact layers of indium tin oxide nanowires for light-emitting devices

Thin layers of indium tin oxide are widely used as transparent coatings and electrodes in solar energy cells, flat-panel displays, antireflection coatings, radiation protection and lithium-ion battery materials, because they have the characteristics of low resistivity, strong absorption at ultraviolet wavelengths, high transmission in the visible, high reflectivity in the far-infrared and strong attenuation in the microwave region. However, there is often a trade-off between electrical conductivity and transparency at visible wavelengths for indium tin oxide and other transparent conducting oxides. Here, we report the growth of layers of indium tin oxide nanowires that show optimum electronic and photonic properties and demonstrate their use as fully transparent top contacts in the visible to near-infrared region for light-emitting devices.