Strategy for Enhancing the Dielectric Constant of Organic Semiconductors Without Sacrificing Charge Carrier Mobility and Solubility

Current organic semiconductors for organic photovoltaics (OPV) have relative dielectric constants (relative permittivities, epsilon(r)) in the range of 2-4. As a consequence, Coulombically bound electron-hole pairs (excitons) are produced upon absorption of light, giving rise to limited power conversion efficiencies. We introduce a strategy to enhance epsilon(r) of well-known donors and acceptors without breaking conjugation, degrading charge carrier mobility or altering the transport gap. The ability of ethylene glycol (EG) repeating units to rapidly reorient their dipoles with the charge redistributions in the environment was proven via density functional theory (DFT) calculations. Fullerene derivatives functionalized with triethylene glycol side chains were studied for the enhancement of epsilon(r) together with poly(p-phenylene vinylene) and diketo-pyrrolopyrrole based polymers functionalized with similar side chains. The polymers showed a doubling of epsilon(r) with respect to their reference polymers in identical backbone. Fullerene derivatives presented enhancements up to 6 compared with phenyl-C-61-butyric acid methyl ester (PCBM) as the reference. Importantly, the applied modifications did not affect the mobility of electrons and holes and provided excellent solubility in common organic solvents.

Role of boron diffusion in CoFeB/MgO magnetic tunnel junctions

Several scientific issues concerning the latest generation read heads for magnetic storage devices, based on CoFeB/MgO/CoFeBmagnetic tunnel junctions (MTJs) are known to be controversial, including such fundamental questions as to the behavior and the role of B in optimizing the physical properties of these devices. Quantitatively establishing the internal structures of several such devices with different annealing conditions using hard x-ray photoelectron spectroscopy, we resolve these controversies and establish that the B diffusion is controlled by the capping Ta layer, though Ta is physically separated from the layer with B by several nanometers. While explaining this unusual phenomenon, we also provide insight into why the tunneling magnetoresistance (TMR) is optimized at an intermediate annealing temperature, relating it to B diffusion, coupled with our studies based on x-ray diffraction and magnetic studies.

Cocrystals of Hydrochlorothiazide: Solubility and Diffusion/Permeability Enhancements through Drug-Coformer Interactions

Hydrochlorothiazide (HCT) is a diuretic and a BCS class IV drug with low solubility and low permeability, exhibiting poor oral absorption. The present study attempts to improve the physicochemical properties of the drug using a crystal engineering approach with cocrystals. Such multicomponent crystals of HCT with nicotinic acid (NIC), nicotinamide (NCT), 4-aminobenzoic acid (PABA), succinamide (SAM), and resorcinol (RES) were prepared using liquid-assisted grinding, and their solubilities in pH 7.4 buffer were evaluated. Diffusion and membrane permeability were studied using a Franz diffusion cell. Except for the SAM and NIC cocrystals, all other binary systems exhibited improved solubility. All of the cocrystals showed improved diffusion/membrane permeability compared to that of HCT with the exception of the SAM cocrystal. When the solubility was high, as in the case of PABA, NCT, and RES cocrystals, the flux/permeability dropped slightly. This is in agreement with the expected interplay between solubility and permeability. Improved solubility/permeability is attributed to new drug-coformer interactions. Cocrystals of SAM, however, showed poor solubility and flux This cocrystal contains a primary sulfonamide dimer synthon similar to that of HCT polymorphs, which may be a reason for its unusual behavior. Hirshfeld surface analysis was carried out in all cases to determine whether a correlation exists between cocrystal permeability and drug-coformer interactions.

Nonlinear Optical Properties and Temperature-Dependent UV-Vis Absorption and Photoluminescence Emission in 2D Hexagonal Boron Nitride Nanosheets

Recently, a lot of interest has been centred on the optical properties of hexagonal boron nitride (h-BN), which has a similar lattice structure to graphene. Interestingly, h-BN has a wide bandgap and is biocompatible, so it has potential applications in multiphoton bioimaging, if it can exhibit large nonlinear optical (NLO) properties. However, extensive investigation into the NLO properties of h-BN have not been done so far. Here, NLO properties of 2D h-BN nanosheets (BNNS) are reported for the first time, using 1064-nm NIR laser radiation with a pulse duration of 10 ns using the Z-scan technique. The reverse saturable absorption occurs in aqueous colloidal solutions of BNNS with a very large two-photon absorption cross section (sigma(2PA)) of approximate to 57 x 10(-46) cm(4) s(-1) photon(-1). Also, by using UV-Vis absorption spectroscopy, the temperature coefficient of the bandgap (dE(g)/dT) of BNNS is determined to be 5.9 meV K-1. Further defect-induced photoluminescence emission in the UV region is obtained in the 283-303 K temperature range, under excitations of different wavelengths. The present report of large sigma(2PA) combined with stability and biocompatibility could open up new possibilities for the application of BNNS as a potential optical material for multiphoton bioimaging and advanced photonic devices.

Boron and Nitrogen Co-doped Carbon Nanoparticles as Photoluminescent Probes for Selective and Sensitive Detection of Picric Acid

Here, we report the synthesis of boron and nitrogen Co-doped carbon nanoparticles (BN-CNPs) by a hydrothermal method using sucrose, boric acid, and urea as the precursors. The BN-CNPs show excellent photoluminescence with a quantum yield of similar to 14.2% in aqueous solution and can be used as photoluminescent probes for selective and sensitive detection of picric acid (PA). PA quenches the photoluminescence signal remarkably, while other explosives cause a little quenching confirming the high selectivity of BN-CNPs. The sensitivity toward PA sensing is high at pH 7 and increases with temperature. The detection limit as well as the sensitivity are shown to improve by adding NaCl to the PA. The low detection limit can be as low as 10 nM at room temperature and pH 7, which indicates the BN-CNPs are superior as compared to other luminescent probes reported in the literature.

Enhancement in Strain Hardening on Boron Addition in As-Cast Ti-6Al-4V Alloy

It has been previously reported that the addition of boron to Ti-6Al-4V results in significant refinement of the as-cast microstructure and enhancement in the strain hardening. However, the mechanism for the latter effect has not been adequately studied. The aim of this study was to understand the reasons for the enhancement in room temperature strain hardening on addition of boron to as cast Ti-6Al-4V alloy. A study was conducted on slip transmission using SEM, TEM, optical profilometry and four point probe resistivity measurements on un-deformed and deformed samples of Ti-6Al-4V-xB with five levels of boron. Optical profilometry was used to quantify the magnitude of offsets on slip traces which in turn provided information about the extent of planar or multiple slip. Studies on deformed samples reveal that while lath boundaries appear to easily permit dislocation slip transmission, colony boundaries are potent barriers to slip. From TEM studies it was also observed that while alloys containing lower boron underwent planar slip, deformation was more homogeneous in higher boron alloys due to multiple slip resulting from large number of colony boundaries. Multiple slip is also proposed to be the prime cause of the enhanced strain hardening.

Structure-mechanical property correlations in mechanochromic luminescent crystals of boron difluoride dibenzoylmethane derivatives

The structure and mechanical properties of crystalline materials of three boron difluoride dibenzoylmethane (BF(2)dbm) derivatives were investigated to examine the correlation, if any, among mechanochromic luminescence (ML) behaviour, solid-state structure, and the mechanical behaviour of single crystals. Qualitative mechanical deformation tests show that the crystals of BF(2)dbm(Bu-t)(2) can be bent permanently, whereas those of BF(2)dbm(OMe)(2) exhibit an inhomogeneous shearing mode of deformation, and finally BF(2)dbmOMe crystals are brittle. Quantitative mechanical analysis by nanoindentation on the major facets of the crystals shows that BF(2)dbm(Bu-t)(2) is soft and compliant with low values of elastic modulus, E, and hardness, H, confirming its superior suceptibility for plastic deformation, which is attributed to the presence of a multitude of slip systems in the crystal structure. In contrast, both BF(2)dbm(OMe)(2) and BF(2)dbmOMe are considerably stiffer and harder with comparable E and H, which are rationalized through analysis of the structural attributes such as the intermolecular interactions, slip systems and their relative orientation with respect to the indentation direction. As expected from the qualitative mechanical behaviour, prominent ML was observed in BF(2)dbm(Bu-t)(2), whereas BF(2)dbm(OMe)(2) exhibits only a moderate ML and BF(2)dbmOMe shows no detectable ML, all examined under identical conditions. These results confirm that the extent of ML in crystalline organic solid-state fluorophore materials can be correlated positively with the extent of plasticity (low recovery). In turn, they offer opportunities to design new and improved efficient ML materials using crystal engineering principles.

Boron-doped carbon nanoparticles: Size-independent color tunability from red to blue and bioimaging applications

Here, we report the hydrothermal synthesis of boron-doped CNPs (B-CNPs) with different size/atomic percentage of doping and size-independent color tunability from red to blue. The variation of size/atomic percentage of B is achieved by simply varying the reaction time, while the color tunability is obtained by diluting the solution. With dilution, the luminescence spectra are not only blue-shifted, the intensity increases as well. The huge blue-shift in the emission energy (similar to 1 eV) is believed to be due to the increase in the interparticle distance. The quantum yield with optimum dilution is found to increase with boron doping though it is very low as compared to CNPs and nitrogen-doped CNPs. Finally, we show that B-CNPs with a quantum yield of 0.5% can be used for bioimaging applications. (C) 2015 Elsevier Ltd. All rights reserved.

First principles DFT investigation Of Yttrium-decorated Boron-Nitride Nanotube: Electronic Structure and Hydrogen Storage

The electronic structure and hydrogen storage capability of Yttrium-doped BNNTs has been theoretically investigated using first principles density functional theory (DFT). Yttrium atom prefers the hollow site in the center of the hexagonal ring with a binding energy of 0.8048eV. Decorating by Y makes the system half-metallic and magnetic with a magnetic moment of 1.0 mu(B). Y decorated Boron-Nitride (8,0) nanotube can adsorb up to five hydrogen molecules whose average binding energy is computed as 0.5044eV. All the hydrogen molecules are adsorbed with an average desorption temperature of 644.708 K. Taking that the Y atoms can be placed only in alternate hexagons, the implied wt% comes out to be 5.31%, a relatively acceptable value for hydrogen storage materials. Thus, this system can serve as potential hydrogen storage medium.

Boron clusters in luminescent materials

In recent times, luminescent materials with tunable emission properties have found applications in almost all aspects of modern material sciences. Any discussion on the recent developments in luminescent materials would be incomplete if one does not account for the versatile photophysical features of boron containing compounds. Apart from triarylboranes and tetra-coordinate borate dyes, luminescent materials consisting of boron clusters have also found immense interest in recent times. Recent studies have unveiled the opportunities hidden within boranes, carboranes and metalloboranes, etc. as active constituents of luminescent materials. From simple illustrations of luminescence, to advanced applications in LASERs, OLEDs and bioimaging, etc., the unique features of such compounds and their promising versatility have already been established. In this review, recent revelations about the excellent photophysical properties of such materials are discussed.

Stimuli and shape responsive `boron-containing' luminescent organic materials

Recent advancements of material science and its applications have been immensely influenced by the modern development of organic luminescent materials. Among all organic luminogens, boron containing compounds have already established their stature as one of the indispensable classes of luminescent dyes. Boron, in its various forms e. g. triarylboranes, borate dyes and boron clusters, has attracted considerable attention owing to its several unique and excellent photophysical features. In very recent times, beyond the realms of solution-state studies, luminescent boron-containing compounds have emerged as a large and versatile class of stimuli responsive materials. Based on several fundamental concepts of chemistry, researchers have come up with an admirable variety of boron-containing materials with AIE (aggregation-induced emission), mechano-responsive luminescence, thermoresponsive-luminescence as well as a number of purely organic phosphorescent materials and other standalone examples. The unique chemical as well as physical properties of boron-containing compounds are largely responsible for the development of such materials. In this review these new findings are brought together.

Influence of surfactant solubility on the deformation and breakup of a bubble or capillary jet in a viscous fluid

In a previous study [M. Hameed, J. Fluid Mech. 594, 307 (2008)] the authors investigated the influence of insoluble surfactant on the evolution of a stretched, inviscid bubble surrounded by a viscous fluid via direct numerical simulation of the Navier-Stokes equations, and showed that the presence of surfactant can cause the bubble to contract and form a quasisteady slender thread connecting parent bubbles, instead of proceeding directly toward pinch-off as occurs for a surfactant-free bubble. Insoluble surfactant significantly retards pinch-off and the thread is stabilized by a balance between internal pressure and reduced capillary pressure due to a high concentration of surfactant that develops during the initial stage of contraction. In the present study we investigate the influence of surfactant solubility on thread formation. The adsorption-desorption kinetics for solubility is in the diffusion controlled regime. A long-wave model for the evolution of a capillary jet is also studied in the Stokes flow limit, and shows dynamics that are similar to those of the evolving bubble. With soluble surfactant, depending on parameter values, a slender thread forms but can pinch-off later due to exchange of surfactant between the interface and exterior bulk flow. © 2009 American Institute of Physics.

Efficient Gate-tunable light-emitting device made of defective boron nitride nanotubes: from ultraviolet to the visible

Boron nitride is a promising material for nanotechnology applications due to its two-dimensional graphene-like, insulating, and highly-resistant structure. Recently it has received a lot of attention as a substrate to grow and isolate graphene as well as for its intrinsic UV lasing response. Similar to carbon, one-dimensional boron nitride nanotubes (BNNTs) have been theoretically predicted and later synthesised. Here we use first principles simulations to unambiguously demonstrate that i) BN nanotubes inherit the highly efficient UV luminescence of hexagonal BN; ii) the application of an external perpendicular field closes the electronic gap keeping the UV lasing with lower yield; iii) defects in BNNTS are responsible for tunable light emission from the UV to the visible controlled by a transverse electric field (TEF). Our present findings pave the road towards optoelectronic applications of BN-nanotube-based devices that are simple to implement because they do not require any special doping or complex growth

Transport Properties And Induced Voltage In The Structure Of Water-Filled Single-Walled Boron-Nitrogen Nanotubes

Density functional theory/molecular dynamics simulations were employed to give insights into the mechanism of voltage generation based on a water-filled single-walled boron-nitrogen nanotube (SWBNNT). Our calculations showed that (1) the transport properties of confined water in a SWBNNT are different from those of bulk water in view of configuration, the diffusion coefficient, the dipole orientation, and the density distribution, and (2) a voltage difference of several millivolts would generate between the two ends of a SWBNNT due to interactions between the water dipole chains and charge carriers in the tube. Therefore, this structure of a water-filled SWBNNT can be a promising candidate for a synthetic nanoscale power cell as well as a practical nanopower harvesting device.