Measurement of contact voltage drop and resistance in organic solar cells

Bulk heterojunction organic solar cells based on poly[4,7-bis(3- dodecylthiophene-2-yl) benzothiadiazole-co-benzothiadiazole] and [6,6]-phenyl C71-butyric acid methyl ester are investigated. A prominent kink is observed in the fourth quadrant of the current density-voltage (J-V) response. Annealing the active layer prior to cathode deposition eliminates the kink. The kink is attributed to an extraction barrier. The J-V response in these devices is well described by a power law. This behavior is attributed to an imbalance in charge carrier mobility. An expected photocurrent for the device displaying a kink in the J-V response is determined by fitting to a power law. The difference between the expected and measured photocurrent allows for the determination of a voltage drop within the device. Under simulated 1 sun irradiance, the peak voltage drop and contact resistance at short circuit are 0.14 V and 90 Ω, respectively. © 2012 American Institute of Physics.

Biodiesel production from non-edible beauty leaf (Calophyllum Inophyllum) oil : process optimization using response surface methodology (RSM)

In recent years, the beauty leaf plant (Calophyllum Inophyllum) is being considered as a potential 2nd generation biodiesel source due to high seed oil content, high fruit production rate, simple cultivation and ability to grow in a wide range of climate conditions. However, however, due to the high free fatty acid (FFA) content in this oil, the potential of this biodiesel feedstock is still unrealized, and little research has been undertaken on it. In this study, transesterification of beauty leaf oil to produce biodiesel has been investigated. A two-step biodiesel conversion method consisting of acid catalysed pre-esterification and alkali catalysed transesterification has been utilized. The three main factors that drive the biodiesel (fatty acid methyl ester (FAME)) conversion from vegetable oil (triglycerides) were studied using response surface methodology (RSM) based on a Box-Behnken experimental design. The factors considered in this study were catalyst concentration, methanol to oil molar ratio and reaction temperature. Linear and full quadratic regression models were developed to predict FFA and FAME concentration and to optimize the reaction conditions. The significance of these factors and their interaction in both stages was determined using analysis of variance (ANOVA). The reaction conditions for the largest reduction in FFA concentration for acid catalysed pre-esterification was 30:1 methanol to oil molar ratio, 10% (w/w) sulfuric acid catalyst loading and 75 °C reaction temperature. In the alkali catalysed transesterification process 7.5:1 methanol to oil molar ratio, 1% (w/w) sodium methoxide catalyst loading and 55 °C reaction temperature were found to result in the highest FAME conversion. The good agreement between model outputs and experimental results demonstrated that this methodology may be useful for industrial process optimization for biodiesel production from beauty leaf oil and possibly other industrial processes as well.

Transcriptional pathway signatures predict MEK addiction and response to selumetinib (AZD6244)

Selumetinib (AZD6244, ARRY-142886) is a selective, non-ATP-competitive inhibitor of mitogen-activated protein/extracellular signal-regulated kinase kinase (MEK)-1/2. The range of antitumor activity seen preclinically and in patients highlights the importance of identifying determinants of response to this drug. In large tumor cell panels of diverse lineage, we show that MEK inhibitor response does not have an absolute correlation with mutational or phospho-protein markers of BRAF/MEK, RAS, or phosphoinositide 3-kinase (PI3K) activity. We aimed to enhance predictivity by measuring pathway output through coregulated gene networks displaying differential mRNA expression exclusive to resistant cell subsets and correlated to mutational or dynamic pathway activity. We discovered an 18-gene signature enabling measurement of MEK functional output independent of tumor genotype. Where the MEK pathway is activated but the cells remain resistant to selumetinib, we identified a 13-gene signature that implicates the existence of compensatory signaling from RAS effectors other than PI3K. The ability of these signatures to stratify samples according to functional activation of MEK and/or selumetinib sensitivity was shown in multiple independent melanoma, colon, breast, and lung tumor cell lines and in xenograft models. Furthermore, we were able to measure these signatures in fixed archival melanoma tumor samples using a single RT-qPCR-based test and found intergene correlations and associations with genetic markers of pathway activity to be preserved. These signatures offer useful tools for the study of MEK biology and clinical application of MEK inhibitors, and the novel approaches taken may benefit other targeted therapies.

Self-reflection as an intervention to influence achievement goal orientations and intrinsic motivation

In the context of physical activity, intrinsic motivation refers to the inherent satisfaction associated with participation in the activity. Interest-enjoyment, perceived competence, and effort have been identified as three underlying components of intrinsic motivation. Achievement goal theory stipulates that achievement goals guide our beliefs and behavior. The two main achievement goal orientations identified in the sport and physical activity literature are task and ego orientations. A person with a strong task orientation defines success in self-referenced terms, as improving one’s own performance or mastering new skills. Someone with a strong ego orientation defines success normatively, as being better than others. The majority of research suggests that having a strong task orientation is a good thing, whether with regard to motivationally adaptive responses, sources of sport confidence, students’ satisfaction with learning, or the use of cognitive and self-regulatory strategies. Although the literature supporting the potential benefits of having a strong task orientation is vast, considerably less research has tested interventions designed to strengthen task orientations and intrinsic motivation. A climate that emphasises individual mastery has resulted in increased interest-enjoyment and perceived competence, whereas an emphasis on competition and comparison with others has resulted in a decrease in interest-enjoyment and an increase in tension-pressure. One possible intervention is the use of structured self-reflection. Using self-reflection sheets that cause respondents to focus on specific elements of technique or skills, and rate one’s own performance, should theoretically promote a task focus. Hanrahan suggested that engaging in self-reflection may enhance intrinsic motivation. Perceived competence could be positively affected, as self-analysis and self-monitoring have been found to positively influence the acquisition of physical skills. The purpose of this study was to determine if the use of structured self-reflection in community dance classes would influence achievement goal orientations or levels of intrinsic motivation.

Electropolymerisation of catalytically active PEDOT from an ionic liquid on a flexible carbon cloth using a sandwich cell configuration

We report the electropolymerization of poly(3,4-ethylenedioxythiopene) (PEDOT) from an ionic liquid, butyl-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (C4mpyrTFSI) onto flexible carbon cloth electrodes. A continuous, homogeneous and well adhered coating of the individual cloth fibres is achieved by employing a sandwich cell arrangement where the carbon cloth which is soaked with electrolyte is placed between two indium tin oxide electrodes isolated from each other by a battery separator. The resultant PEDOT modified carbon cloth electrode demonstrates excellent activity for the oxygen reduction reaction which is due to the doping level, conductivity and morphology of the PEDOT layer and is also tolerant to the presence of methanol in the electrolyte. This simple approach therefore offers a route to fabricate flexible polymer electrodes that could be used in various electronic applications.

Time-independent charge carrier mobility in a model polymer:fullerene organic solar cell

The technique of photo-CELIV (charge extraction by linearly increasing voltage) is one of the more straightforward and popular approaches to measure the faster carrier mobility in measurement geometries that are relevant for operational solar cells and other optoelectronic devices. It has been used to demonstrate a time-dependent photocarrier mobility in pristine polymers, attributed to energetic relaxation within the density of states. Conversely, in solar cell blends, the presence or absence of such energetic relaxation on transport timescales remains under debate. We developed a complete numerical model and performed photo-CELIV experiments on the model high efficiency organic solar cell blend poly[3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-naphthalene] (PDPP-TNT):[6,6]-phenyl-C71-butyric-acid-methyl-ester (PC70BM). In the studied solar cells a constant, time-independent mobility on the scale relevant to charge extraction was observed, where thermalisation of photocarriers occurs on time scales much shorter than the transit time. Therefore, photocarrier relaxation effects are insignificant for charge transport in these efficient photovoltaic devices.

Multifunctional SA-PProDOT binder for lithium ion batteries

An environmentally benign, highly conductive, and mechanically strong binder system can overcome the dilemma of low conductivity and insufficient mechanical stability of the electrodes to achieve high performance lithium ion batteries (LIBs) at a low cost and in a sustainable way. In this work, the naturally occurring binder sodium alginate (SA) is functionalized with 3,4-propylenedioxythiophene-2,5-dicarboxylic acid (ProDOT) via a one-step esterification reaction in a cyclohexane/dodecyl benzenesulfonic acid (DBSA)/water microemulsion system, resulting in a multifunctional polymer binder, that is, SA-PProDOT. With the synergetic effects of the functional groups (e.g., carboxyl, hydroxyl, and ester groups), the resultant SA-PProDOT polymer not only maintains the outstanding binding capabilities of sodium alginate but also enhances the mechanical integrity and lithium ion diffusion coefficient in the LiFePO4 (LFP) electrode during the operation of the batteries. Because of the conjugated network of the PProDOT and the lithium doping under the battery environment, the SA-PProDOT becomes conductive and matches the conductivity needed for LiFePO4 LIBs. Without the need of conductive additives such as carbon black, the resultant batteries have achieved the theoretical specific capacity of LiFePO4 cathode (ca. 170 mAh/g) at C/10 and ca. 120 mAh/g at 1C for more than 400 cycles.

Optimized multilayer indium-free electrodes for organic photovoltaics

Flexible multilayer electrodes that combine high transparency, high conductivity, and efficient charge extraction have been deposited, characterised and used as the anode in organic solar cells. The anode consists of an AZO/Ag/AZO stack plus a very thin oxide interlayer whose ionization potential is fine-tuned by manipulating its gap state density to optimise charge transfer with the bulk heterojunction active layer consisting of poly(n-3- hexylthiophene-2,5-diyl) and phenyl-C61-butyric acid methyl ester (P3HT:BC61BM). The deposition method for the stack was compatible with the low temperatures required for polymer substrates. Optimisation of the electrode stack was achieved by modelling the optical and electrical properties of the device and a power conversion efficiency of 2.9% under AM1.5 illumination compared to 3.0% with an ITO-only anode and 3.5% for an ITO:PEDOT electrode. Dark I-V reverse bias characteristics indicate very low densities of occupied buffer states close to the HOMO level of the hole conductor, despite observed ionization potential being high enough. Their elimination should raise efficiency to that with ITO:PEDOT.

Organic photovoltaics using thin gold film as an alternative anode to indium tin oxide

Indium Tin Oxide (ITO) is the most commonly used anode as a transparent electrode and more recently as an anode for organic photovoltaics (OPVs). However, there are significant drawbacks in using ITO which include high material costs, mechanical instability including brittleness and poor electrical properties which limit its use in low-cost flexible devices. We present initial results of poly(3-hexylthiophene): phenyl-C61-butyric acid methyl ester OPVs showing that an efficiency of 1.9% (short-circuit current 7.01 mA/cm2, open-circuit voltage 0.55 V, fill factor 0.49) can be attained using an ultra thin film of gold coated glass as the device anode. The initial I-V characteristics demonstrate that using high work function metals when the thin film is kept ultra thin can be used as a replacement to ITO due to their greater stability and better morphological control.

P-n junction organic photovoltaics fabricated by all solution processing

We have prepared p-n junction organic photovoltaic cells using an all solution processing method with poly(3-hexylthiophene) (P3HT) as the donor and phenyl-C 61-butyric acid methyl ester (PCBM) as the acceptor. Interdigitated donor/acceptor interface morphology was observed in the device processed with the lowest boiling point solvent for PCBM used in this study. The influences of different solvents on donor/acceptor morphology and respective device performance were investigated simultaneously. The best device obtained had characteristically rough interface morphology with a peak to valley value ∼15 nm. The device displayed a power conversion efficiency of 1.78%, an open circuit voltage (V oc) 0.44 V, a short circuit current density (J sc) 9.4 mA/cm 2 and a fill factor 43%.

Room-temperature tilted-target sputtering deposition of highly transparent and low sheet resistance Al doped ZnO electrodes

Target-tilted room temperature sputtering of aluminium doped zinc oxide (AZO) provides transparent conducting electrodes with sheet resistances of <10 Ω □-1 and average transmittance in the visible region of up to 84%. The properties of the AZO electrode are found to be strongly dependent on the target-tilting angle and film thickness. The AZO electrodes showed comparable performance to commercial indium tin oxide (ITO) electrodes in organic photovoltaic (OPV) devices. OPV devices containing a bulk heterojunction active layer comprised of poly(3-n-hexylthiophene) (P3HT):phenyl-C61-butyric acid methyl ester (PCBM) and an AZO transparent conducting electrode had a power conversion efficiency (PCE) of up to 2.5% with those containing ITO giving a PCE of 2.6%. These results demonstrate that AZO films are a good alternative to ITO for transparent conducting electrodes.

Effects of biodiesel chemical composition on the chemical and physical properties of the primary and secondary diesel particulate matter

This thesis improves our insight towards the effects of using biodiesels on the particulate matter emission of diesel engines and contributes to our understanding of their potential adverse health effects. The novelty of this project is the use of biodiesel fuel with controlled chemical composition that enables us to relate changes of physiochemical properties of particles to specific properties of the biodiesel. For the first time, the possibility of a correlation of the volatility and the Reactive Oxygen Species concentration of the particles is investigated versus the saturation, oxygen content and carbon chain length of the fuel.

Charge transport studies in donor-acceptor block copolymer PDPP-TNT and PC71BM based inverted organic photovoltaic devices processed in room conditions

Diketopyrrolopyrole-naphthalene polymer (PDPP-TNT), a donor-acceptor co-polymer, has shown versatile behavior demonstrating high performances in organic field-effect transistors (OFETs) and organic photovoltaic (OPV) devices. In this paper we report investigation of charge carrier dynamics in PDPP-TNT, and [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) bulk-heterojunction based inverted OPV devices using current density-voltage (J-V) characteristics, space charge limited current (SCLC) measurements, capacitance-voltage (C-V) characteristics, and impedance spectroscopy (IS). OPV devices in inverted architecture, ITO/ZnO/PDPP-TNT:PC71BM/MoO3/Ag, are processed and characterized at room conditions. The power conversion efficiency (PCE) of these devices are measured ∼3.8%, with reasonably good fill-factor 54.6%. The analysis of impedance spectra exhibits electron’s mobility ∼2 × 10−3 cm2V−1s−1, and lifetime in the range of 0.03-0.23 ms. SCLC measurements give hole mobility of 1.12 × 10−5 cm2V−1s−1, and electron mobility of 8.7 × 10−4 cm2V−1s−1.

IgE+ B cells are scarce, but allergen-specific B cells with a memory phenotype circulate in patients with allergic rhinitis

Background Despite the critical role of immunoglobulin E (IgE) in allergy, circulating IgE+ B cells are scarce. Here, we describe in patients with allergic rhinitis B cells with a memory phenotype responding to a prototypic aeroallergen. Methods Fifteen allergic rhinitis patients with grass pollen allergy and 13 control subjects were examined. Blood mononuclear cells stained with carboxyfluorescein diacetate succinimidyl ester (CFSE) were cultured with Bahia grass pollen. Proliferation and phenotype were assessed by multicolour flow cytometry. Results In blood of allergic rhinitis patients with high serum IgE to grass pollen, most IgEhi cells were CD123+ HLA-DR- basophils, with IgE for the major pollen allergen (Pas n 1). Both B and T cells from pollen-allergic donors showed higher proliferation to grass pollen than nonallergic donors (P = 0.002, and 0.010, respectively), whereas responses to vaccine antigens and mitogen did not differ between groups. Allergen-driven B cells that divided rapidly (CD19mid CD3- CFSElo) showed higher CD27 (P = 0.008) and lower CD19 (P = 0.004) and CD20 (P = 0.004) expression than B cells that were slow to respond to allergen (CD19hi CD3- CFSEmid). Moreover, rapidly dividing allergen-driven B cells (CD19mid CFSElo CD27hi) showed higher expression of the plasmablast marker CD38 compared with B cells (CD19hi CFSEmid CD27lo) that were slow to divide. Conclusion Patients with pollen allergy but not control donors have a population of circulating allergen-specific B cells with the phenotype and functional properties of adaptive memory B-cell responses. These cells could provide precursors for allergen-specific IgE production upon allergen re-exposure. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.