Synergistic effect of reactor chemistry and compressive stress on dislocation bending during GaN growth

The synergistic effect of compressive growth stresses and reactor chemistry, silane presence, on dislocation bending at the very early stages of GaN growth has been studied using in-situ stress measurements and cross-sectional transmission electron microscopy. A single 100 nm Si-doped GaN layer is found to be more effective than a 1 mu m linearly graded AlGaN buffer layer in reducing dislocation density and preventing the subsequent layer from transitioning to a tensile stress. 1 mu m crack-free GaN layers with a dislocation density of 7 x 10(8)/cm(2), with 0.13 nm surface roughness and no enhancement in n-type background are demonstrated over 2 inch substrates using this simple transition scheme. (C) 2013 AIP Publishing LLC.

Role of electrolyte chemistry on electronic and in vitro electrochemical properties of micro-arc oxidized titania films on Cp Ti

The primary objective of the present work was to study the electronic and in vitro electrochemical properties of micro-arc oxidized titania films on Cp Ti, fabricated independently in various electrolyte solutions consisting of anions such as phosphate (PO43-), borate (B4O72-), citrate (C6H5O73-) and silicate (SiO32-). Further the role of anions on the structural, morphological and compositional properties of the fabricated films was studied. All the titania films were developed by micro-arc oxidation (MAO) technique for a fixed treatment time of 8 min under constant current mode. The surface morphology, elemental distribution, composition and structural characteristics of the films were assessed by scanning electron microscope (SEM) equipped with energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) techniques. The thermodynamic and kinetic corrosion properties of the films were studied under simulated body fluid (SBF) conditions (pH 7.4 and 37 degrees C) by conducting chronopotentiometric and potentiodynamic polarization tests. Electrochemical impedance spectroscopy (EIS) coupled with equivalent circuit modelling was carried out to analyse the frequency response and Mott-Schottky analysis was performed to study the semiconducting (electronic) properties of the films. Salt spray fog accelerated corrosion test was conducted for 168h as per ASTM B117 standard to corroborate the corrosion and semiconducting properties of the samples based on the visual examination. The XRD results showed that the transformation from the metastable anatase phase to the thermodynamically stable rutile phase and the crystalline growth of the respective phases were strongly influenced by the addition of anions. The SEM-EDS results demonstrated that the phosphorous (P) content in the films varied from 2.4 at% to 5.0 at% indicating that the amount of P in the films could be modified by adding an appropriate electrolyte additive. The electrochemical corrosion test results showed that the film fabricated in citrate (C6H5O73-) containing electrolyte is thermodynamically and kinetically more stable compared to that of all the others. The results of the Mott-Schottky analysis indicated that all the fabricated films showed an n-type semiconducting behaviour and the film developed in citrate (C6H5O73-) containing electrolyte exhibited the lowest donor concentration and the most negative flat band potential that contributed to its highest corrosion resistance in SBF solution. The results of the salt spray accelerated corrosion tests were in agreement with those obtained from the electrochemical and Mott-Schottky analysis.

Information content of molecular graph and prediction of gas phase thermal entropy of organic compounds

Entropy is a fundamental thermodynamic property that has attracted a wide attention across domains, including chemistry. Inference of entropy of chemical compounds using various approaches has been a widely studied topic. However, many aspects of entropy in chemical compounds remain unexplained. In the present work, we propose two new information-theoretical molecular descriptors for the prediction of gas phase thermal entropy of organic compounds. The descriptors reflect the bulk and size of the compounds as well as the gross topological symmetry in their structures, all of which are believed to determine entropy. A high correlation () between the entropy values and our information-theoretical indices have been found and the predicted entropy values, obtained from the corresponding statistically significant regression model, have been found to be within acceptable approximation. We provide additional mathematical result in the form of a theorem and proof that might further help in assessing changes in gas phase thermal entropy values with the changes in molecular structures. The proposed information-theoretical molecular descriptors, regression model and the mathematical result are expected to augment predictions of gas phase thermal entropy for a large number of chemical compounds.

Diketopyrrolopyrrole-Based Conjugated Polymers and Small Molecules for Organic Ambipolar Transistors and Solar Cells

The present highlight discusses major work in the synthesis of low bandgap diketopyrrolopyrrole (DPP)-based polymers with donor-acceptor-donor (D-A-D) approach and their application in organic electronics. It examines the past and recent significant advances which have led to development of low bandgap DPP-based materials with phenyl and thiophene as donors. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4241-4260

Glycidyl azide polymer crosslinked through triazoles by click chemistry: curing, mechanical and thermal properties

Glycidyl azide polymer (GAP) was cured through click chemistry by reaction of the azide group with bispropargyl succinate (BPS) through a 1,3-dipolar cycloaddition reaction to form 1,2,3-triazole network. The properties of GAP-based triazole networks are compared with the urethane cured GAP-systems. The glass transition temperature (T-g), tensile strength, and modulus of the system increased with crosslink density, controlled by the azide to propargyl ratio. The triazole incorporation has a higher T-g in comparison to the GAP-urethane system (T-g-20 degrees C) and the networks exhibit biphasic transitions at 61 and 88 degrees C. The triazole curing was studied using Differential Scanning Calorimetry (DSC) and the related kinetic parameters were helpful for predicting the cure profile at a given temperature. Density functional theory (DFT)-based theoretical calculations implied marginal preference for 1,5-addition over 1,4-addition for the cycloaddition between azide and propargyl group. Thermogravimetic analysis (TG) showed better thermal stability for the GAP-triazole and the mechanism of decomposition was elucidated using pyrolysis GC-MS studies. The higher heat of exothermic decomposition of triazole adduct (418kJmol(-1)) against that of azide (317kJmol(-1)) and better mechanical properties of the GAP-triazole renders it a better propellant binder than the GAP-urethane system.

Physics and chemistry of CdTe/CdS thin film heterojunction photovoltaic devices: fundamental and critical aspects

Among the armoury of photovoltaic materials, thin film heterojunction photovoltaics continue to be a promising candidate for solar energy conversion delivering a vast scope in terms of device design and fabrication. Their production does not require expensive semiconductor substrates and high temperature device processing, which allows reduced cost per unit area while maintaining reasonable efficiency. In this regard, superstrate CdTe/CdS solar cells are extensively investigated because of their suitable bandgap alignments, cost effective methods of production at large scales and stability against proton/electron irradiation. The conversion efficiencies in the range of 6-20% are achieved by structuring the device by varying the absorber/window layer thickness, junction activation/annealing steps, with more suitable front/back contacts, preparation techniques, doping with foreign ions, etc. This review focuses on fundamental and critical aspects like: (a) choice of CdS window layer and CdTe absorber layer; (b) drawbacks associated with the device including environmental problems, optical absorption losses and back contact barriers; (c) structural dynamics at CdS-CdTe interface; (d) influence of junction activation process by CdCl2 or HCF2Cl treatment; (e) interface and grain boundary passivation effects; (f) device degradation due to impurity diffusion and stress; (g) fabrication with suitable front and back contacts; (h) chemical processes occurring at various interfaces; (i) strategies and modifications developed to improve their efficiency. The complexity involved in understanding the multiple aspects of tuning the solar cell efficiency is reviewed in detail by considering the individual contribution from each component of the device. It is expected that this review article will enrich the materials aspects of CdTe/CdS devices for solar energy conversion and stimulate further innovative research interest on this intriguing topic.

Magnetic and dielectric interactions in nano zinc ferrite powder: Prepared by self-sustainable propellant chemistry technique

The structural, magnetic and dielectric properties of nano zinc ferrite prepared by the propellant chemistry technique are studied. The PXRD measurement at room temperature reveal that the compound is in cubic spinel phase, belong to the space group Fd (3) over barm. The unit cell parameters have been estimated from Rietveld refinement. The calculated force constants from FTIR spectrum corresponding to octahedral and tetrahedral sites at 375 and 542 cm(-1) are 6.61 x 10(2) and 3.77 x 10(2) N m(-1) respectively; these values are slightly higher compared to the other ferrite systems. Magnetic hysteresis and EPR spectra show superparamagnetic property nearly to room temperature due to comparison values between magnetic anisotropy energy and the thermal energy. The calculated values of saturation magnetization, remenant magnetization, coercive field and magnetic moment supports for the existence of multi domain particles in the sample. The temperature dependent magnetic field shows the spin freezing state at 30 K and the blocking temperature at above room temperature. The frequency dependent dielectric interactions show the variation of dielectric constant, dielectric loss and impedance as similar to other ferrite systems. The AC conductivity in the prepared sample is due to the presence of electrons, holes and polarons. The synthesized material is suitable for nano-electronics and biomedical applications. (C) 2014 Elsevier B.V. All rights reserved.

Performance of an ionomer blend-nanocomposite as an effective gas barrier material for organic devices

A new, flexible, gas barrier material has been synthesized by exfoliating organically modified nano-clays (MMT) in the blends of Surlyn (PEMA) using a copolymer of vinyl alcohol (EVOH) and demonstrated as a gas barrier material. The materials were characterized by Fourier transform infra red (FTIR) and UV-visible spectroscopy, differential scanning calorimetry (DSC), thermo-gravimetric analysis (TGA) and tensile studies. The oxygen and water-vapor permeabilities of the fabricated films were determined by calcium degradation test and a novel permeability setup based on cavity ring down spectroscopy, respectively. Hierarchical simulations of these materials helped us to understand the effect of intermolecular interactions on diffusivities of oxygen and water molecules in these materials. Schottky structured poly(3-hexylthiophene) based organic devices were encapsulated with the fabricated films and aging studies were carried under accelerated conditions. Based on permeability test results and accelerated aging studies, the fabricated PEMA/EVOH/MMT composites were found to be effective in decreasing the permeabilities for gases by about two orders of magnitude and maintaining the lifetime of organic devices.

C. N. R. Rao and the Growth of Solid State and Materials Chemistry as a Central Domain of Research

In celebrating Professor C. N. R. Rao's 80th birthday, this article recalls his singular contributions to solid state and materials chemistry for about sixty years. In so doing, the article also traces the growth of the field as a central domain of research in chemical sciences from its early origins in Europe. Although Rao's major work lies in solid state and materials chemistry - a field which he started and nurtured in India while its importance was being recognized internationally - his contributions to other areas of chemistry (and physics), viz., molecular spectroscopy, phase transitions, fullerenes, graphene, nanomaterials and multiferroics are equally significant. Illustrative examples of his work devoted to rare earth and transition metal oxides, defects and nonstoichiometry, metal-insulator transitions, investigation of crystal and electronic structures of a variety of solids by means of electron microscopies and photoelectron spectroscopy, superconducting cuprates, magnetoresistive manganites, multiferroic metal oxides of various structures and, last but not the least, development of new strategies for chemical synthesis of a wide variety of solids including nanomaterials and framework solids in different dimensionalities, are highlighted. The article also captures his exemplary role as a science teacher, science educationist and institution builder in post-Independence India.

In-situ Stabilization of Tin Nanoparticles in Porous Carbon Matrix derived from Metal Organic Framework: High Capacity and High Rate Capability Anodes for Lithium-ion Batteries

It is a formidable challenge to arrange tin nanoparticles in a porous matrix for the achievement of high specific capacity and current rate capability anode for lithium-ion batteries. This article discusses a simple and novel synthesis of arranging tin nanoparticles with carbon in a porous configuration for application as anode in lithium-ion batteries. Direct carbonization of synthesized three-dimensional Sn-based MOF: K2Sn2(1,4-bdc)(3)](H2O) (1) (bdc = benzenedicarboxylate) resulted in stabilization of tin nanoparticles in a porous carbon matrix (abbreviated as Sn@C). Sn@C exhibited remarkably high electrochemical lithium stability (tested over 100 charge and discharge cycles) and high specific capacities over a wide range of operating currents (0.2-5 Ag-1). The novel synthesis strategy to obtain Sn@C from a single precursor as discussed herein provides an optimal combination of particle size and dispersion for buffering severe volume changes due to Li-Sn alloying reaction and provides fast pathways for lithium and electron transport.

Model for triplet state engineering in organic light emitting diodes

Engineering the position of the lowest triplet state (T-1) relative to the first excited singlet state (S-1) is of great importance in improving the efficiencies of organic light emitting diodes and organic photovoltaic cells. We have carried out model exact calculations of substituted polyene chains to understand the factors that affect the energy gap between S-1 and T-1. The factors studied are backbone dimerisation, different donor-acceptor substitutions, and twisted geometry. The largest system studied is an 18 carbon polyene which spans a Hilbert space of about 991 x 10(6). We show that for reverse intersystem crossing process, the best system involves substituting all carbon sites on one half of the polyene with donors and the other half with acceptors. (C) 2014 AIP Publishing LLC.

Mechanochemical Synthesis of Amide Functionalized Porous Organic Polymers

Two porous organic polymers decorated with the amide functionality were synthesized mechanochemically and their properties were compared with the ones prepared by conventional solution mediated method. All the POPs were subjected to gas and water vapor sorption studies. The mechanochemically synthesized POPs have less surface area and show moderate adsorption properties compared to the solution mediated POPs. The amide based POPs show remarkable stability in water and concentrated acids.

Construction of Bis-pyrazole Based Co(II) Metal-Organic Frameworks and Exploration of Their Chirality and Magnetic Properties

In continuation of our interest in pyrazole based multifunctional metal-organic frameworks (MOFs), we report herein the construction of a series of Co(II) MOFs using a bis-pyrazole ligand and various benzene polycarboxylic acids. Employment of different acids has resulted in different architectures ranging from a two-dimensional grid network, porous nanochannels with interesting double helical features such as supramolecular chicken wire, to three-dimensional diamondoid networks. One of the distinguishing features of the network is their larger dimensions which can be directly linked to a relatively larger size of the ligand molecule. Conformational flexibility of the ligand also plays a decisive role in determining both the dimensionality and topology of the final structure. Furthermore, chirality associated with helical networks and magnetic properties of two MOFs have also been investigated.

Organic fragments from graphene oxide: Isolation, characterization and solvent effects

As-prepared graphene oxide (GO) contains oxidative debris which can be washed using basic solutions. We present the isolation and characterization of these debris. Dynamic light scattering (DLS) is used to monitor the separation of the debris in various solvents in the presence of different protic and aprotic alkylamino bases. The study reveals that the debris are rich in carbonyl functional groups and water is an essential component for separation and removal of the debris from GO under oxidative reaction conditions.