Furan substituted diketopyrrolopyrrole and thienylenevinylene based low band gap copolymer for high mobility organic thin film transistors

A novel solution processable donor-acceptor (D-A) based low band gap polymer semiconductor poly{3,6-difuran-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4- c]pyrrole-1,4-dione-alt-thienylenevinylene} (PDPPF-TVT), was designed and synthesized by a Pd-catalyzed Stille coupling route. An electron deficient furan based diketopyrrolopyrrole (DPP) block and electron rich thienylenevinylene (TVT) donor moiety were attached alternately in the polymer backbone. The polymer exhibited good solubility, film forming ability and thermal stability. The polymer exhibits wide absorption bands from 400 nm to 950 nm (UV-vis-NIR region) with absorption maximum centered at 782 nm in thin film. The optical band gap (Eoptg) calculated from the polymer film absorption onset is around 1.37 eV. The π-energy band level (ionization potential) calculated by photoelectron spectroscopy in air (PESA) for PDPPF-TVT is around 5.22 eV. AFM and TEM analyses of the polymer reveal nodular terrace morphology with optimized crystallinity after 200 °C thermal annealing. This polymer exhibits p-channel charge transport characteristics when used as the active semiconductor in organic thin-film transistor (OTFT) devices. The highest hole mobility of 0.13 cm 2 V -1 s -1 is achieved in bottom gate and top-contact OTFT devices with on/off ratios in the range of 10 6-10 7. This work reveals that the replacement of thiophene by furan in DPP copolymers exhibits such a high mobility, which makes DPP furan a promising block for making a wide range of promising polymer semiconductors for broad applications in organic electronics.

Engineering thin film semiconductor gas sensors to increase sensitivity and decrease operation temperature

Thin film nanostructured gas sensors typically operate at temperatures above 400°C, but lower temperature operation is highly desirable, especially for remote area field sensing as this reduces significantly power consumption. We have investigated a range of sensor materials based on both pure and doped tungsten oxide (mainly focusing on Fe-doping), deposited using both thermal evaporation and electron-beam evaporation, and using a variety of post-deposition annealing. The films show excellent sensitivity at operating temperatures as low as 150°C for detection of NO2. There is a definite relationship between the sensitivity and the crystallinity and nanostructure obtained through the deposition and heat treatment processes, as well as variations in the conductivity caused both by doping and heat treatmetn. The ultimate goal of this work is to control the sensing properties, including selectivity to specific gases through the engineering of the electronic properties and the nanostructure of the films.

Graphene-based supercapacitor with carbon nanotube film as highly efficient current collector

Flexible graphene-based thin film supercapacitors were made using carbon nanotube (CNT) films as current collectors and graphene films as electrodes. The graphene sheets were produced by simple electrochemical exfoliation, while the graphene films with controlled thickness were prepared by vacuum filtration. The solid-state supercapacitor was made by using two graphene/CNT films on plastic substrates to sandwich a thin layer of gelled electrolyte. We found that the thin graphene film with thickness <1 μm can greatly increase the capacitance. Using only CNT films as electrodes, the device exhibited a capacitance as low as ~0.4 mF cm−2, whereas by adding a 360 nm thick graphene film to the CNT electrodes led to a ~4.3 mF cm−2 capacitance. We experimentally demonstrated that the conductive CNT film is equivalent to gold as a current collector while it provides a stronger binding force to the graphene film. Combining the high capacitance of the thin graphene film and the high conductivity of the CNT film, our devices exhibited high energy density (8–14 Wh kg−1) and power density (250–450 kW kg−1).

Selective electrochemical epinephrine sensor using self-assembled monomolecular film of 1,8,15,22-tetraaminophthalocyanatonickel(II) on gold electrode

This article describes the highly sensitive and selective determination of epinephrine (EP) using self-assembled monomolecular film (SAMF) of 1,8,15,22-tetraamino-phthalocyanatonickel(II) (4α-NiIITAPc) on Au electrode. The 4α-NiIITAPc SAMF modified electrode was prepared by spontaneous adsorption of 4α-NiIITAPc from dimethylformamide solution. The modified electrode oxidizes EP at less over potential with enhanced current response in contrast to the bare Au electrode. The standard heterogeneous rate constant (k°) for the oxidation of EP at 4α-NiIITAPc SAMF modified electrode was found to be 1.94×10−2 cm s−1 which was much higher than that at the bare Au electrode. Further, it was found that 4α-NiIITAPc SAMF modified electrode separates the voltammetric signals of ascorbic acid (AA) and EP with a peak separation of 250 mV. Using amperometric method the lowest detection limit of 50 nM of EP was achieved at SAMF modified electrode. Simultaneous amperometric determination of AA and EP was also achieved at the SAMF modified electrode. Common physiological interferents such as uric acid, glucose, urea and NaCl do not interfere within the potential window of EP oxidation. The present 4α-NiIITAPc SAMF modified electrode was also successfully applied to determine the concentration of EP in commercially available injection.

Determination of l-dopa using electropolymerized 3,3′,3″,3‴-tetraaminophthalocyanatonickel(II) film on glassy carbon electrode

Electropolymerized film of 3,3′,3″,3‴-tetraaminophthalocyanatonickel(II) (p-NiIITAPc) on glassy carbon (GC) electrode was used for the selective and stable determination of 3,4-dihydroxy-l-phenylalanine (l-dopa) in acetate buffer (pH 4.0) solution. Bare GC electrode fails to determine the concentration of l-dopa accurately in acetate buffer solution due to the cyclization reaction of dopaquinone to cyclodopa in solution. On the other hand, p-NiIITAPc electrode successfully determines the concentration of l-dopa accurately because the cyclization reaction was prevented at this electrode. It was found that the electrochemical reaction of l-dopa at the modified electrode is faster than that at the bare GC electrode. This was confirmed from the higher heterogeneous electron transfer rate constant (k0) of l-dopa at p-NiIITAPc electrode (3.35 × 10−2 cm s−1) when compared to that at the bare GC electrode (5.18 × 10−3 cm s−1). Further, it was found that p-NiIITAPc electrode separates the signals of ascorbic acid (AA) and l-dopa in a mixture with a peak separation of 220 mV. Lowest detection limit of 100 nM was achieved at the modified electrode using amperometric method. Common physiological interferents like uric acid, glucose and urea does not show any interference within the potential window of l-dopa oxidation. The present electrode system was also successfully applied to estimate the concentration of l-dopa in the commercially available tablets.

High performance all-carbon thin film supercapacitors

We fabricated high performance supercapacitors by using all carbon electrodes, with volume energy in the order of 10−3 Whcm−3, comparable to Li-ion batteries, and power densities in the range of 10 Wcm−3, better than laser-scribed-graphene supercapacitors. All-carbon supercapacitor electrodes are made by solution processing and filtering electrochemically-exfoliated graphene sheets mixed with clusters of spontaneously entangled multiwall carbon nanotubes. We maximize the capacitance by using a 1:1 weight ratio of graphene to multi-wall carbon nanotubes and by controlling their packing in the electrode film so as to maximize accessible surface and further enhance the charge collection. This electrode is transferred onto a plastic-paper-supported double-wall carbon nanotube film used as current collector. These all-carbon thin films are combined with plastic paper and gelled electrolyte to produce solid-state bendable thin film supercapacitors. We assembled supercapacitor cells in series in a planar configuration to increase the operating voltage and find that the shape of our supercapacitor film strongly affects its capacitance. An in-line superposition of rectangular sheets is superior to a cross superposition in maintaining high capacitance when subject to fast charge/discharge cycles. The effect is explained by addressing the mechanism of ion diffusion into stacked graphene sheets.

Design of high mobility DPP-based polymer semiconductors for organic thin film transistors

π-Conjugated polymers are the most promising semiconductor materials to enable printed organic thin film transistors (OTFTs) due to their excellent solution processability and mechanical robustness. However, solution-processed polymer semiconductors have shown poor charge transport properties mainly originated from the disordered polymer chain packing in the solid state as compared to the thermally evaporated small molecular organic semiconductors. The low charge carrier mobility, typically < 0.1 cm2 /V.s, of polymer semiconductors poses a challenge for most intended applications such as displays and radio-frequency identification (RFID) tags. Here we present our recent results on the dike topyrrolopyrrole (DPP)-based polymers and demonstrate that when DPP is combined with appropriate electron donating moieties such as thiophene and thienothiophene, very high charge carrier mobility values of ~1 cm2/V.s could be achieved.

Scheimpflug imaging of the post lens tear film during contact lens wear

A new imaging methodology is described to visualise the post lens tear film (PLTF) during contact lens wear. A rotating-Scheimpflug camera in combination with sodium fluorescein allows evaluation of the PLTF for different contact lens modalities, including mini-scleral, rigid gas permeable (RGP) and soft contact lenses. This imaging technique provides an extension of the instrument’s current functionality. The potential advantages and limitations of the technique are discussed.

The culture wars of climate change

Of late, there has been a growth in cultural expression about climate change – with the rise of climate fiction (‘cli-fi’); art and photography responding to changes in nature; musical anthems about climate change; plays and dramas about climate change; and environmental documentaries, and climate cinema. Drawing comparisons to past controversies over cultural funding, this paper considers the cultural wars over climate change. This article considers a number of cultural fields. Margaret Atwood made an important creative and critical contribution to the debate over climate change. The work examines Ian McEwan's novel, Solar, a tragi-comedy about authorship, invention, intellectual property, and climate science. After writing a history of Merchants of Doubt, Naomi Oreskes and Erik Conway have experimented with fiction – as well as history. This article focuses upon artistic works about climate change. It analyses James Balog’s work with the Extreme Ice Survey, which involved photography of glaciers under retreat in a warming world. The work was turned into a documentary called Chasing Ice. It also considers the artistic project of 350.org 'to transform the human rights and environmental issues connected to climate change into powerful art that gets people to stop, think and act.' The paper examines musical storytelling in respect of climate change. The paper explores dramatic works about climate change including Steve Waters' The Contingency Plan, Stephen Emmott's Ten Billion, and Andrew Bovell's When the Rain Stops Falling and Hannie Rayson’s Extinction. The paper also examines the role of documentary film-making. It also considers the cinematographic film, Beasts of the Southern Wild. Such a survey will enable a consideration of the larger question of whether creative art about climate change matters; and whether it is deserving of public funding.

Optimization of organic solar cells with thin film Au as anode

Optical transmittance and conductivity for thin metallic films, such as Au, are two inversely related and extremely important parameters for its application in organic photovoltaics as the front electrode. We report our findings on how these parameters have been optimized to attain maximum possible efficiencies by fabricating organic solar cells with thin Au film anodes of differing optical transmittances and consequently due to scaling at the nanolevel, varying electrical conductivities. There was an extraordinary improvement in the overall solar cell efficiency (to the order of 49%) when the Au thin film transmittance was increased from 38% to 54%. Surface morphologies of these thin films also have an effect on the critical parameters including, Voc, Jsc and FF.