Quantum Dots and Nanoroads of Graphene Embedded in Hexagonal Boron Nitride

The quest for novel two-dimensional materials has led to the discovery of hybrids where graphene and hexagonal boron nitride (h-BN) occur as phase-separated domains. Using first-principles calculations, we study the energetics and electronic and magnetic properties of such hybrids in detail. The formation energy of quantum dot inclusions (consisting of n carbon atoms) varies as 1/root n, owing to the interface. The electronic gap between the occupied and unoccupied energy levels of quantum dots is also inversely proportional to the length scale, 1/root n-a feature of confined Dirac fermions. For zigzag nanoroads, a combination of the intrinsic electric field caused by the polarity of the h-BN matrix and spin polarization at the edges results in half-metallicity; a band gap opens up under the externally applied ``compensating'' electric field. For armchair nanoroads, the electron confinement opens the gap, different among three subfamilies due to different bond length relaxations at the interfaces, and decreasing with the width.

Synthesis, Structures, and Magnetic Behavior of a Series of Copper(II) Azide Polymers of Cu-4 Building Clusters and Isolation of a New Hemiaminal Ether as the Metal Complex

Four new neutral copper azido polymers, Cu-4(N-3)(8)(L-1)(2)](n) (1), Cu-4(N-3)(8)(L-2)(2)](n) (2), Cu-4(N-3)(8)(L-3)(2)](n) (3), and Cu-9(N-3)(18)(L-4)(4)](n) (4) L1-4 are formed in situ by reacting pyridine-2-carboxaldehyde with 22-(methylamino)ethyl]pyridine (mapy, L-1), N,N-dimethylethylenediamine (N,N-dmen, L-2), N,N-diethylethylenediamine (N,N-deen, L-3), and N,N,2,2-tetramethylpropanediamine (N,N,2,2-tmpn, L-4)], have been synthesized by using 0.5 mol equiv of the chelating tridentate ligands with Cu-(NO3)(2)center dot 3H(2)O and an excess of NaN3. Single-crystal X-ray structures show that the basic unit of these complexes, especially 1-3, contains very similar Cu-4(II) building blocks. The overall structure of 3 is two-dimensional, while the other three complexes are one-dimensional in nature. Complex 1 represents a unique example containing hemiaminal ether arrested by copper(R). Complexes 1 and 2 have a rare bridging azido pathway: both end-on and end-to-end bridging azides between a pair of Cu-II centers. Cryomagnetic susceptibility measurements over a wide range of temperature exhibit dominant ferromagnetic behavior in all four complexes. Density functional theory calculations (B3LYP functional) have been performed on complexes 1-3 to provide a qualitative theoretical interpretation of their overall ferromagnetic behavior.

Electrical and Optical Properties of Diketopyrrolopyrrole-Based Copolymer Interfaces in Thin Film Devices

Two donor acceptor diketopyrrolopyrrole (DPP)-based copolymers (PDPP-BBT and TDPP-BBT) have been synthesized for their application in organic devices such as metal-insulator semiconductor (MIS) diodes and field-effect transistors (FETs). The semiconductor-dielectric interface was characterized by capacitance-voltage and conductance-voltage methods. These measurements yield an interface trap density of 4.2 x 10(12) eV(-1) cm(-2) in TDPP-BBT and 3.5 x 10(12) eV(-1) cm(-2) in PDPP-BBT at the flat-band voltage. The FETs based on these spincoated DPP copolymers display p-channel behavior with hole mobilities of the order 10(-3) cm(2)/(V s). Light scattering studies from PDPP-BBT FETs show almost no change in the Raman spectrum after the devices are allowed to operate at a gate voltage, indicating that the FETs suffer minimal damage due to the metal-polymer contact or the application of an electric field. As a comparison Raman intensity profile from the channel-Au contact layer in pentacene FETs are presented, which show a distinct change before and after biasing.

Microstructural and dielectric properties of KCl-added bismuth vanadate ceramics

The effect of KCI addition on the microstructural, structural and dielectric properties of bismuth vanadate, Bi2VO5.5 (BiV) has been examined. The average grain size of BN ceramics increases with increase in KCl content (from an average grain size of TO to 80 mu m) as a result of the increased liquid-phase formation of KCI, at the grain boundaries. Differential scanning calorimetry (DSC) carried out on the KCl-added samples indicates an upward shift in the transition temperature (T-c), from 723 K (for BN) to 734 K (for 5 mol% KCl-added BiV). On further increase in the KCI content, T-c shifts down to about 722 K for 10 mol%. This trend is consistent with that of the lattice strain data. The relative permittivity as well as the dielectric loss decrease by more than half of the original values upon the addition of KCI. The relative permittivities of the KCl-added ceramics are comparable with the values predicted by the logarithmic mixture rule. Impedance analyses suggest that the grain boundary resistance of the KCl-added BiV ceramics is higher by two orders of magnitude than that of BN ceramics. The KCl-added BN ceramics exhibit ferroelectric domains and the domain density decreases as the grain boundary region is approached.

Optical and structural properties of reactive ion beam sputter deposited CeO2 films

Optical and structural properties of reactive ion beam sputter deposited CeO2 films as a function of oxygen partial pressures (P-O2) and substrate temperatures (T-s) have been investigated. The films deposited at ambient temperature with P-O2 of 0.01 Pa have shown a refractive index of 2.36 which increased to 2.44 at 400 degrees C. Refractive index and extinction coefficient are sensitive up to a T-s of similar to 200 degrees C. Raman spectroscopy and X-ray diffraction (XRD) have been used to characterise the structural properties. A preferential orientation of (220) was observed up to a T-s of 200 degrees C and it changed to (200) at 400 degrees C: and above. Raman line broadening, peak shift and XRD broadening indicate the formation of nanocrystalline phase for the films deposited up to a substrate temperature of 300 degrees C. However, crystallinity of the films were better for T-s values above 300 degrees C. In general both optical and structural properties were unusual compared to the films deposited by conventional electron beam evaporation, but were similar in some aspects to those deposited by ion-assisted deposition. Apart from thermal effects, this behavior is also attributed to the bombardment of backscattered ions/neutrals on the growing film as well as the higher kinetic energy of the condensing species, together resulting in increased packing density. (C) 1997 Elsevier Science S.A.

Relation between integral and partial properties of ternary solutions along different composition trajectories

The relations between partial and integral properties of ternary solutions along composition trajectories suggested by Kohler, Colinet and Jacob, and along an arbitrary path are derived. The chemical potentials of the components are related to the slope of integral free energy by expressions involving the binary compositions generated by the intersections of the composition trajectory with the sides of the ternary triangle. Only along the Kohler composition trajectory it is possible to derive the integral free energy from the variation of the chemical potential of a single component with composition or vice versa. Along all other paths the differential of the integral free energy is related to two chemical potentials. The Gibbs-Duhem integration proposed by Darken for the ternary system uses the Kohler isogram. The relative merits of different limits for integration are discussed.

Spectroscopic, redox and photophysical properties of push-pull fluoroarylporphyrins

Novel fluoroarylporphyrins bearing electron donor dimethylamino groups in the meso-aryl positions and an electron acceptor nitro group on one of the pyrrole carbons exhibit significant solvent dependent fluorescence spectra and time-resolved emission properties. These effects are suggestive of intramolecular charge transfer (ICT) in the singlet excited state of these porphyrins. Electrochemical redox behaviour of these porphyrins showed the presence of substantial donor-acceptor interactions in the nitro-amino porphyrins.

Structural and transport properties of high energy ion irradiated YBCO

The effects of 100 MeV Oxygen and 200 MeV Silver ions on the structural and transport properties of YBCO thin films are reported. Both normal state and superconducting properties were studied on Laser ablated and high pressure oxygen sputtered films. Precise electrical resistance and critical current measurements near T-c were made and the data obtained were analysed in the light of existing models of para-coherence near T-c and the other aspects of radiation damage arising from microstructural studies such as atomic force microscopy (AFM). There was evidence of sputtering by high energy ions from AFM measurement. (C) 1998 Elsevier Science Ltd. All rights reserved.

Studies on structural and electrical properties of barium strontium titanate thin films developed by metallo-organic decomposition

Thin films of barium strontium titanate (BST) including BaTiO3 and SrTiO3 end members were deposited using the metallo-organic decomposition (MOD) technique. Processing parameters such as nonstoichiometry, annealing temperature and time, film thickness and doping concentration were correlated with the structural and electrical properties of the films. A random polycrystalline structure was observed for all MOD films under the processing conditions in this study. The microstructures of the films showed multi-grains structure through the film thickness. A dielectric constant of 563 was observed for (Ba0.7Sr0.3)TiO3 films rapid thermal annealed at 750 degrees C for 60 s. The dielectric constant increased with annealing temperature and film thickness, while the dielectric constant could reach the bulk values for thicknesses as thin as similar to 0.3 mu m. Nonstoichiometry and doping in the films resulted in a lowering of the dielectric constant. For near-stoichiometric films, a small dielectric dispersion obeying the Curie-von Schweidler type dielectric response was observed. This behavior may be attributed to the presence of the high density of disordered grain boundaries. All MOD processed films showed trap-distributed space-charge limited conduction (SCLC) behavior with slope of similar to 7.5-10 regardless of the chemistry and processing parameter due to the presence of main boundaries through the film thickness. The grain boundaries masked the effect of donor-doping, so that all films showed distributed-trap SCLC behavior without discrete-traps. Donor-doping could significantly improve the time-dependent dielectric breakdown behavior of BST thin films, mostly likely due to the lower oxygen vacancy concentration resulted from donor-doping. From the results of charge storage density, leakage current and time-dependent dielectric breakdown behavior, BST thin films are found to be promising candidates for 64 and 256Mb ULSI DRAM applications. (C) 1997 Elsevier Science S.A.

``Clickable'', Trifunctional Magnetite Nanoparticles and Their Chemoselective Biofunctionalization

A multifunctional iron oxide based nanoformulation for combined cancer-targeted therapy and multimodal imaging has been meticulously designed and synthesized using a chemoselective ligation approach. Novel superparamagnetic magnetite nanoparticles simultaneously functionalized with amine, carboxyl, and azide groups were fabricated through a sequence of stoichiometrically controllable partial succinylation and Cu (II) catalyzed diazo transfer on the reactive amine termini of 2-aminoethylphosphonate grafted magnetite nanoparticles (MNPs). Functional moieties associated with MNP surface were chemoselectively conjugated with rhodamine B isothiocyanate (RITC), propargyl folate (FA), and paclitaxel (PTX) via tandem nucleophic addition of amine to isothithiocyanates, Cu (I) catalyzed azide-alkyne click chemistry and carbodiimide-promoted esterification. An extensive in vitro study established that the bioactives chemoselectively appended to the magnetite core bequeathed multifunctionality to the nanoparticles without any loss of activity of the functional molecules. Multifunctional nanoparticles, developed in the course of the study, could selectively target and induce apoptosis to folate-receptor (FR) overexpressing cancer cells with enhanced efficacy as compared to the free drug. In addition, the dual optical and magnetic properties of the synthesized nanoparticles aided in the real-time tracking of their intracellular pathways also as apoptotic events through dual fluorescence and MR-based imaging.

Radiation induced modifications on microstructure and related properties of high temperature superconductor YBCO

Role of swift heavy ion irradiation on the modification of transport and structural properties of high temperature superconductors is studied. Good quality YBCO thin films prepared by high pressure oxygen sputtering and laser ablation were used in this investigation. Resistivity and atomic force microscopy (AFM) were mainly used to probe superconducting and microstructural modifications resulted from the irradiation of high energy and heavy ions like 100 MeV oxygen and 200 MeV silver. Radiation induced sputtering or erosion is likely to be a major disastrous component of such high energy irradiation that could be powerful in masking phase coherence effects, atleast in grain boundaries. The extent of damage/nature of defects other than columnar defects produced by swift heavy ions is discussed in the light of AFM measurements. The effect of high energy oxygen ion irradiation is anomalous. A clear annealing effect at higher doses is seen. (C) 1999 Elsevier Science B.V. All rights reserved.

Spectral, thermal and electrical properties of poly(o- and m-toluidine) PVC blends prepared by solution blending

Poly(o-toluidine) (POT) and poly(m-toluidine) (PMT) blends with polyvinylchloride (PVC) of five different compositions have been prepared by solution blending. The POT-PVC and PMT-PVC blends were prepared using THF as a solvent in which POT-HNO3, PMT-HNO3 bases and PVC are soluble. The blends have been characterized by spectral, thermal and electrical measurements. The results indicate the formation of blends at all the compositions presently studied. The thermal stability of the POT-PVC and PMT-PVC blends is higher than that of POT-HNO3 and PMT-HNO3 salts, respectively. Using the present method, POT/PMT can conveniently be blended with 30% wt/wt of PVC without significant loss in its conductivity. (C) 1998 Elsevier Science Ltd. All rights reserved.

Structural, dielectric and optical properties of lithium borate-bismuth tungstate glass-ceramicsc

Glasses in the system (1 - x)Li2B4O7-xBi(2)WO(6) (0.1 less than or equal to x less than or equal to 0.35) were prepared by splat quenching technique. Powder X-ray diffraction (XRD) and differential thermal analysis (DTA) were employed to characterize the as-quenched glasses. High-resolution transmission electron microscopy (HR TEM) revealed the presence of fine, nearly spherical crystallites of Bi2WO6 varying from 1.5 to 20 nm in size, depending on x in the as-quenched glasses. The glasses (corresponding to x = 0.3) heat-treated at 723 K for 6 h gave rise to a clear crystalline phase of Bi2WO6 embedded in the Li2B4O7 glass matrix, as observed by X-ray studies. The dielectric constants of the as-quenched glasses as well as the glass-ceramics decreased with increase in frequency (40Hz-100 kHz) at 300 K, and the value obtained for the glass-ceramic (x = 0.2) is in agreement with the values predicted using Maxwell's model and the logarithmic mixture rule. The dielectric constants for both the as-quenched glass and the glass-ceramic increased with increase in temperature (300 - 873 K) and exhibited anomalies close to the onset of the crystallization temperature of the host glass matrix. The optical transmission properties:of these glass-ceramics were found to be compositional dependant. (C) 2000 Elsevier Science Ltd.

Structural dielectric and optical properties of SrB4O7-BaO-TiO2 glasses

Glass samples with compositions (100-2x)SrB4O7-xBaO-xTiO(2) (10 less than or equal to x less than or equal to 40) were prepared by conventional melt quenching and the influence of the addition of BaO-TiO2 on the structural, dielectric and optical properties of SBO glasses was studied The molar volume, glass transition temperature and the optical polarisability of the glass samples were found to decrease with increase in BaO-TiO2 content while the refractive index and optical band gap increase with increase in BaO-TiO2 content.

Molecular self-assembly of cadmium-triazolate complexes via hydrogen bonding: Synthesis, structures and photoluminescent properties

Two new cadmium coordination polymers namely Cd(HAmTrz-COO)(4)(NH4+)(2)] 1; and Cd(HAmTrz)(2)I-2](n) 2; (HAmTrz-COOH = 3-amino-1,2,4-triazole-5-carboxylic acid), have been prepared based on HAmTrz-COOH as ligand. The crystal structures of 1 and 2 have been determined by single-crystal X-ray diffraction technique. In coordination-complex 1 four triazole ligands coordinate via N1 nitrogen leading to a tetrahedral geometry around cadmium ion, while in 2 the ligand prefers to coordinate to the metal in a bidentate bridging mode. The structures of both the coordination polymers can be envisaged as 3D hydrogen bonded networks. Thermogravimetric analysis shows that 2 is more stable than 1 owing to different coordination numbers of cadmium atoms. Photoluminescence properties of both the compounds have been investigated in the solid state. (C) 2011 Elsevier B.V. All rights reserved.