Bismuth carboxylates with Brucite- and Fluorite-related structures: synthesis structure and properties

Three new compounds of bismuth, C4N2H10]center dotBi(C7H4NO4)(C7H3NO4)]center dot H2O, I, Bi(C5H3N2O4) (C5H2N2O4)], II, and Bi(mu(2)-OH)(C7H3NO4)], III, have been prepared by the reaction between bismuth nitrate and heterocyclic aromatic dicarboxylic acids, 2,6-pyridinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, and 3,4-pyridinedicarboxylic acid, respectively, under hydrothermal conditions. The structures of all the compounds have linkages between Bi2O2 and the corresponding dicarboxylate forming a simple molecular unit in I, a bilayer arrangement in II, and a three-dimensional extended structure in III. The topological arrangement of the nodal building units in the structures indicates that a brucite-related layer (II) and fluorite-related arrangement (III) can be realized in these structures. By utilizing the secondary interactions, one can correlate the structure of III to a Kagome-related one. The observation of such classical inorganic related structures in the bismuth carboxylates is noteworthy. Lewis acid catalytic studies on the formation of ketal suggest the possible participatory role of the lone pair of electrons. All the compounds are characterized employing elemental analysis, IR, UV-vis, and thermal studies.

Growth and characterization of micro and nanostructures of lead telluride (PbTe) by thermal evaporation method

Lead telluride micro and nanostructures have been grown on silicon and glass substrates by a simple thermal evaporation of PbTe in high vacuum of 3 x 10(-5) mbar. Growth was carried out for two different distances between the evaporation source and the substrates. Synthesized products consist of nanorods and micro towers for 2.4 cm and 3.4 cm of distance between the evaporation source and the substrates respectively. X-ray diffraction and transmission electron microscopy studies confirmed crystalline nature of the nanorods and micro towers. Nanorods were grown by vapor solid mechanism. Each micro tower consists of nano platelets and is capped with spherical catalyst particle at their end, suggesting that the growth proceeds via vapor-liquid-solid (VLS) mechanism. EDS spectrum recorded on the tip of the micro tower has shown the presence of Pb and Te confirming the self catalytic VLS growth of the micro towers. These results open up novel synthesis methods for PbTe nano and microstructures for various applications.

A new approach for understanding ion transport in glasses; example of complex alkali diborate glasses containing lead, bismuth and tellurium oxides

Mechanism of ion transport in glasses continues to be incompletely understood. Several of the theoretical models in vogue fail to rationalize conductivity behaviour when d.c. and a.c. measurements are considered together. While they seem to involve the presence of at least two components in d.c. activation energy, experiments fail to reveal that feature. Further, only minor importance is given to the influence of structure of the glass on the ionic conductivity behaviour. In this paper, we have examined several general aspects of ion transport taking the example of ionically conducting glasses in pseudo binary, yNa(2)B(4)O(7)center dot(1-y) M (a) O (b) (with y = 0 center dot 25-0 center dot 79 and M (a) O (b) = PbO, TeO2 and Bi2O3) system of glasses which have also been recently characterized. Ion transport in them has been studied in detail. We have proposed that non-bridging oxygen (NBO) participation is crucial to the understanding of the observed conductivity behaviour. NBO-BO switching is projected as the first important step in ion transport and alkali ion jump is a subsequent event with a characteristically lower barrier which is, therefore, not observed in any study. All important observations in d.c. and a.c. transport in glasses are found consistent with this model.

Evidence of an intermediate phase in a quaternary Ag bearing telluride glass system using alternating DSC

Alternating Differential Scanning Calorimetric (ADSC) studies on quaternary Ge15Te80-xIn5Agx glasses show the non-reversing enthalpy (Delta H-NR) at T-g to exhibit a broad global minimum in the 8% <= x <= 16% range of Ag, an observation that is taken evidence for existence of an Intermediate Phase (IP) in that range. Glasses at x < 8% are in the flexible phase while those at x > 16% in the stressed-rigid phase. The nature of crystalline phases formed upon crystallization of bulk glasses are elucidated by XRD studies, and reveal presence of Te, GeTe, Ag8GeTe6, AgTe, In2Te3 and In4Te3 phases. These experiments also reveal that the fraction of Ag- bearing phases increases while those of Te- bearing ones decreases with increasing x, suggesting progressive replacement of Te-Te bonds by Ag-Te bonds. (C) 2013 Elsevier Ltd. All rights reserved.

Correlations between mechanical and photoluminescence properties in Eu doped sodium bismuth titanate

Nanoindentation technique is utilized to examine mechanical property variation in Eu doped Na0.5Bi0.5 TiO3 (NBT). Doping levels of Eu in NBT is systematically varied. Dilute doping results in a linear reduction in both modulus and hardness. At higher concentrations, a recovery of the mechanical properties (to undoped NBT values) is observed. These experimental trends mirror variations in the optical emission intensities with Eu concentration. Observed trends are rationalized on the basis of a model, which hypothesizes phase segregation beyond a critical Eu doping level. Such segregation leads to the formation of pure NBT, nano-Eu saturated NBT, and nano-mixed Eu oxides in the microstructure. Pure NBT is optically inactive, while saturated Eu:NBT is a much better emitter when compared to europium oxide. Hence beyond the critical concentration, luminescence signal comes primarily from the saturated Eu:NBT phase. The model presented is supported by nanoindentation, and spectroscopic results. (C) 2013 Elsevier Ltd. All rights reserved.

Effect of ultrasonic treatment on surface crystallization of calcium bismuth borate glasses

Transparent glasses in CaO-Bi2O3-B2O3 system were fabricated via the conventional melt-quenching technique. X-ray powder diffraction (XRD) and differential thermal analysis (DTA) carried out on the as-quenched samples confirmed their amorphous and glassy nature respectively. The surface crystallization behaviour of these glasses with and without ultrasonic surface treatment (UST) was monitored using XRD, optical microscopy and scanning electron microscopy (SEM). The volume fraction, depth of crystallization and the (001) orientation factor for the heat treated samples with and without UST were compared. The ultrasonically-treated samples on subsequent heat treatment were found to crystallize at lower temperatures associated with the highest degree of orientation factor (0.95) in contrast with those of non-UST samples. These surface crystallized glasses were found to exhibit nonlinear optical behaviour emitting green light (532 nm) when they were exposed to the infrared radiation (1064 nm) using Nd:YAG laser.

Voltammetric detection of arsenic on a bismuth modified exfoliated graphite electrode

We present the application of a bismuth modified exfoliated graphite electrode in the detection of arsenic in water. Bismuth film was electrodeposited onto an exfoliated graphite (EG) electrode at a potential of -600 mV. The modification of EG resulted in an increase in the electroactive surface area of the electrode and consequently peak current enhancement in Ru(NH3)(6)(2+/13+) redox probe. Square wave anodic stripping voltammetry was performed with the modified electrode (EG-Bi) in As (III) solutions at the optimum conditions of pH 6, deposition potential of -600 mV and pre-concentration time of 180s. The EG-Bi was able to detect As (III) to the limit of 5 mu g L-1 and was not susceptible to many interfering cations except Cu (II). The EG-Bi is low cost and easy to prepare. (C) 2013 Elsevier Ltd. All rights reserved.

New single-source precursor for bismuth sulfide and its use as low-cost counter electrode material for dye-sensitized solar cells

One new homoleptic Bi(dtc)(3)] (1) (dtc = 4-hydroxypiperdine dithiocarbamate) has been synthesized and characterized by microanalysis, IR, UV-Vis, H-1 and C-13 spectroscopy and X-ray crystallography. The photoluminescence spectrum for the compound in DMSO solution was recorded. The crystal structure of 1 displayed distorted octahedral geometry around the Bi(III) center bonded through sulfur atoms of the dithiocarbamate ligands. TGA indicates that the compound decomposes to a Bi and Bi-S phase system. The Bi and Bi-S obtained from decomposition of the compound have been characterized by pXRD, EDAX and SEM. Solvothermal decomposition of 1 in the absence and presence of two different capping agents yielded three morphologically different Bi2S3 systems which were deployed as counter-electrode in dye-sensitized solar cells (DSSCs). (C) 2015 Elsevier B.V. All rights reserved.

Efficient charge transfer and field-induced tunneling transport in hybrid composite device of organic semiconductor and cadmium telluride quantum dots

Temperature and photo-dependent current-voltage characteristics are investigated in thin film devices of a hybrid-composite comprising of organic semiconductor poly(3,4-ethylenedioxythiophene): polystyrenesulfonate (PEDOT: PSS) and cadmium telluride quantum dots (CdTe QDs). A detailed study of the charge injection mechanism in ITO/PEDOT: PSS-CdTe QDs/Al device exhibits a transition from direct tunneling to Fowler-Nordheim tunneling with increasing electric field due to formation of high barrier at the QD interface. In addition, the hybrid-composite exhibits a huge photoluminescence quenching compared to aboriginal CdTe QDs and high increment in photoconductivity (similar to 400%), which is attributed to the charge transfer phenomena. The effective barrier height (Phi(B) approximate to 0.68 eV) is estimated from the transition voltage and the possible origin of its variation with temperature and photo-illumination is discussed. (C) 2015 AIP Publishing LLC.

Size and temperature dependence of the photoluminescence properties of NIR emitting ternary alloyed mercury cadmium telluride quantum dots

Exciton-phonon coupling and nonradiative relaxation processes have been investigated in near-infrared (NIR) emitting ternary alloyed mercury cadmium telluride (CdHgTe) quantum dots. Organically capped CdHgTe nanocrystals of sizes varying from 2.5-4.2 nm have been synthesized where emission is in the NIR region of 650-855 nm. Temperature-dependent (15-300 K) photoluminescence (PL) and the decay dynamics of PL at 300 K have been studied to understand the photophysical properties. The PL decay kinetics shows the transition from triexponential to biexponential on increasing the size of the quantom dots (QDs), informing the change in the distribution of the emitting states. The energy gap is found to be following the Varshni relation with a temperature coefficient of 2.1-2.8 x 10(-4) eV K-1. The strength of the electron-phonon coupling, which is reflected in the Huang and Rhys factor S, is found in the range of 1.17-1.68 for QDs with a size of 2.5-4.2 nm. The integrated PL intensity is nearly constant until 50 K, and slowly decreases up to 140 K, beyond which it decreases at a faster rate. The mechanism for PL quenching with temperature is attributed to the presence of nonradiative relaxation channels, where the excited carriers are thermally stimulated to the surface defect/trap states. At temperatures of different region (<140 K and 140-300 K), traps of low (13-25 meV) and high (65-140 meV) activation energies seem to be controlling the quenching of the PL emission. The broadening of emission linewidth is found to due to exciton-acoustic phonon scattering and exciton-longitudinal optical (LO) phonon coupling. The exciton-acoustic phonon scattering coefficient is found to be enhanced up to 55 MU eV K-1 due to a stronger confinement effect. These findings give insight into understanding the photophysical properties of CdHgTe QDs and pave the way for their possible applications in the fields of NIR photodetectors and other optoelectronic devices.

Schottky barrier heights of tantalum oxide, barium strontium titanate, lead titanate, and strontium bismuth tantalate

The Schottky barrier heights of various metals on the high permitivity oxides tantalum pentoxide, barium strontium titanate, lead zirconate titanate, and strontium bismuth tantalate have been calculated as a function of the metal work function. It is found that these oxides have a dimensionless Schottky barrier pinning factor S of 0.28-0.4 and not close to 1 because S is controlled by Ti-O-type bonds not Sr-O-type bonds, as assumed in earlier work. The band offsets on silicon are asymmetric with a much smaller offset at the conduction band, so that Ta2O5 and barium strontium titanate are relatively poor barriers to electrons on Si. © 1999 American Institute of Physics.

Schottky barrier heights of tantalum oxide, barium strontium titanate, lead zirconate titanate and strontium bismuth tantalate

Schottky barrier heights of various metals on tantalum pentoxide, barium strontium titanate, lead zirconate-titanate and strontium bismuth tantalate have been calculated as a function of metal work function. These oxides have a dimensionless Schottky barrier pinning factor, S, of 0.28 - 0.4 and not close to 1, because S is controlled by the Ti-O type bonds not Sr-O type bonds, as assumed previously. Band offsets on silicon are asymmetric with much smaller offset at the conduction band, so that Ta2O5 and barium strontium titanate (BST) are relatively poor barriers to electrons on Si.

Bismuth-doped fiber integrated ring laser mode-locked with a nanotube-based saturable absorber

We demonstrate passive mode-locking of a bismuth-doped fiber laser using a singlewall nanotube-based saturable absorber. Stable operation in the all-normal dispersion and average soliton regime is obtained, with an all-fiber integrated format. © 2010 Optical Society of America.