Low bandgap alternating polyfluorene copolymers in plastic photodiodes and solar cells

We report a comparative study of plastic photodiodes using four different copolymers of fluorene, with a variation of alkyl side chain length and chemical structure. Photodiode materials are formed by blending the polymers with a fullerene derivative and spincoating the blend solution. A photovoltage of 1 V is obtained in devices, where the anode is a doped polymer and the cathode is LiF/Al. Monochromatic quantum efficiencies are better than 40% over most of the absorption range, and under solar light AM 1.5 simulation, we reach energy efficiencies beyond 2%. The high fill factors obtained in some of the devices indicate that these are of interest for more elaborate optimisation. Reasons for the benign electrical transport are discussed. PACS 73.50.Pz; 73.61.Ph     

Cavitation: a contributory factor in the transition from symmetric to asymmetric jets in cross-flow nozzles

The structure and evolution of cavitation and its influence on jet patterns from two transparent cross-flow nozzles with holes inclined at 90 degrees (nozzle A) and 80 degrees (nozzle B) to the nozzle axis have been investigated using high-speed motion pictures, flash photography and stroboscopic visualization. At the onset, cavitation inception was in the form of travelling bubbles, which were transported along the flow and clearly detached from the wall. As the flow was increased the bubbles grew and merged into a dense group of bubbles (cloud cavitation), partly unsteady and shedding. Further increasing the flow caused the cavitation at the entrance to transform mainly into a glassy appearance and at this stage the cavitation was well inside the hole and the spray appeared symmetric. When the flow was increased beyond this stage, cavitation extended to the exit of the hole, occupying a significant part of the hole on one side, resulting in a jet that atomized on the side where cavitation was most extensive and a non-atomizing jet on the side with less cavitation. The distribution of cavitation in the hole is very sensitive to the nozzle geometry and it substantially influences the spray dispersion.     

Reversible Hydrophobic Barriers Introduced by Microcontact Printing: Application to Protein Microarrays

Microcontact printing (µCP) has been used to introduce temporary hydrophobic barriers on carboxymethylated dextran (CMD) hydrogels on gold. Among the investigated types of inks, tetraoctadecylammonium bromide (TOAB), electrostatically bound to the CMD layer, provided the most well-defined features both with respect to pattern-definition and reversibility upon exposure to a regeneration solution. The printed patterns were characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), microscopic wetting and imaging null ellipsometry to explore the influence of concentration of ink solution and contact time on the appearance of the printed layer. AFM revealed that the printed TOAB molecules aggregated into clusters rather than into a homogeneous mono- or multilayer on the CMD hydrogel. It was also observed that printed areas of TOAB that are larger than 25µm are inhomogeneous most likely because of an edge transfer lithography (ETL) mechanism. A protein model system based on Protein A-rabbit antimouse Fc was used to evaluate the potential of the patterned surface as a protein microarray chip by means of surface plasmon microscopy (SPM). Moreover, non-specific adsorption of several proteins onto TOAB barriers was also studied using surface plasmon resonance (SPR), and it is evident that undesired adsorption can be eliminated by removing barriers after ligand immobilization, but prior to analyte exposure, by treating the patterned surface with a simple salt regeneration solution.     

Peak purity determination with principal component analysis of high-performance liquid chromatography-diode array detection data

A method is proposed for the determination of chromatographic peak purity by means of principal component analysis (PCA) of high-performance liquid chromatography with diode array detection (HPLC-DAD) data. The method is exemplified with analysis of binary mixtures of lidocaine and prilocaine with different levels of separation. Lidocaine and prilocaine have very similar spectra and the chromatograms used had substantial peak overlap. The samples analysed contained a constant amount of lidocaine and a minor amount of prilocaine (0.02-2 conc.%) and hence the focus was on determining the purity of the lidocaine peak in the presence of much smaller levels of prilocaine. The peak purity determination was made by examination of relative observation residuals, scores and loadings from the PCA decomposition of DAD data over a chromatographic peak. As a reference method, the functions for peak purity analysis in the chromatographic data system used (Chromeleon) were applied. The PCA method showed good results at the same level as the detection limit of baseline-separated prilocaine, outperforming the methods in Chromeleon by a factor of ten. There is a discussion of the interpretation of the result, with some comparisons with evolving factor analysis (EFA). The main advantage of the PCA method for determination of peak purity over methods like EFA lies in its simplicity, short time of calculation and ease of use.     

Structural investigations of polymer electrolyte poly(propylene oxide)-LiClO4 using diffraction experiments and reverse Monte Carlo simulation

The structure of an amorphous polymer electrolyte, poly(propylene oxide) (PPO) complexed with LiClO4, has been studied using reverse Monte Carlo (RMC) simulations. The simulations require no force field but are based on experimental data only, in this case from x-ray and neutron diffraction experiments. Excellent agreement between the experimental data and the structures resulting from the RMC simulation is obtained. Samples with ether-oxygen to lithium concentrations (molar ratios) O:Li=16:1 and 5:1 were studied and compared to results of pure PPO from a previous study. We focus on the effects of the solvated salt on the structure of the polymer matrix, the spatial distribution of ions, and the correlations between the anions and the polymer chains. Analyzing the structures produced in the simulations, we find that for a concentration 16:1, the interchain distance is approximately the same as in pure PPO but more well defined. For a concentration 5:1, we find a larger and less well-defined interchain distance compared to the 16:1 concentration. This signifies that at the 16:1 salt concentration, there is enough free volume in the polymer host to accommodate the ions, and that the solvation of salt induces ordering of the polymer matrix. At the higher salt concentration 5:1, the polymer network must expand and become less ordered to host the ions. We also note, in accordance with previous studies, that the solvation of salt changes the conformation of the polymer chain towards more gauche states. The simulations furthermore reveal marked correlations between the polymer chains and the anions, which we suggest arise predominantly from an interaction mediated via cations, which can simultaneously coordinate both ether oxygens in the polymer chains and anions. Interanionic distances at 5 A, which are consistent with two or more anions being coordinated around the same cation, are also observed. On a larger scale, the RMC structure of PPO-LiClO4 16:1 clearly indicates the presence of salt-rich and salt-depleted domains having a length scale of <20 A. In view of such a heterogeneous structure of PPO-LiClO4 16:1, it is plausible that the increased ordering of the polymer matrix is due to rather well-defined structural arrangements within the salt-rich domains, and that the characteristic interchain distance in the salt-rich domains is similar to that of the pure polymer.     

Rationally designed ligands for asymmetric iridium-catalyzed hydrogenation of olefins

A new class of chiral N,P-ligands for the Ir-catalyzed asymmetric hydrogenation of aryl alkenes has been developed. These new ligands proved to be highly efficient and tolerates a broad range of substrates. The enantiomeric excesses are in the range of the best ever reported. The results can be rationalized with the proposed selectivity model.     

Vanishing magnetic interactions in ferromagnetic thin films

We have used element-specific hysteresis measurements, based on the x-ray magnetic circular dichroism technique, to investigate magnetic trilayer structures composed of Fe and Ni layers. Within a critical regime we have discovered a class of structures in which the exchange interaction, the mechanism responsible for the macroscopic magnetism, can become vanishingly small. The experimental observations are supported by first principles theory and are explained as arising from a cancellation of several competing magnetic interactions. Hence, we have discovered a system with a novel exchange interaction between magnetic layers in direct contact that replaces the conventional exchange interaction in ferromagnets.     

Relaxation time of water's high-density amorphous ice phase

Dielectric relaxation spectroscopy of pressure amorphized hexagonal ice shows that water's high-density amorphous form relaxes in approximately 1 s at 140 K and 1 GPa and that the relaxation is virtually unaffected by pressure. This indicates that the amorph is an ultraviscous liquid above 140 K, the same as would be obtained by supercooling water at 1 GPa through its ice VI phase boundary, and that the glass transition temperature is independent of pressure and close to that of amorphous solid water produced at atmospheric pressure.     

Are pulsar glitches triggered by a superfluid two-stream instability?

Mature neutron stars are expected to have several superfluid components. Strong evidence for this is provided by the glitches that have been observed in dozens of pulsars. We describe a superfluid analog of the two-stream instability that is well known in plasma physics and provide arguments that this instability is likely to be relevant for neutron stars. This is a new physical mechanism which may play a key role in explaining the glitch mechanism and which could also prove to be relevant in laboratory experiments on various superfluid systems.     

First-principle calculations of the experimental vibrational spectrum of a surface adsorbate: anharmonic resonance coupling between fundamental and binary modes

By including relevant physical properties in our modeling of a surface adsorbate system we can, from first principles, correctly calculate all experimentally observed features in the vibrational spectrum of CH3CH2O- and CD3CH2O- adsorbed on Cu(100). That is, we reproduce the number of observed modes, the vibrational frequencies, and intensities of the modes including the presence/absence of binary overtone and combination modes. No scaling was performed. Our calculations show that the anharmonic terms of the potential energy surface of free ethanol are transferrable to the corresponding surface adsorbate, ethoxy, while the harmonic terms are not.