A novel piezoelectric ZnO nanogenerator on flexible metal alloy substrate

In this paper, we report a novel piezoelectric ZnO nanogenerator on flexible metal alloy substrate (Phynox alloy) for energy harvesting and sensing applications. The vertically aligned ZnO nanowires are sandwiched between Au electrodes. The aligned growth of ZnO nanowires have been successfully synthesized on Au coated metal alloy substrate by hydrothermal method at low temperature (95 +/- 1 degrees C). The as-synthesized vertically aligned ZnO nanowires were characterized using FE-SEM. Further, PMMA is spin coated over the aligned ZnO nanowires for the purpose of their long term stability. The fabricated nanogenerator is of size 30mm x 6mm. From energy harvesting point of view, the response of the nanogenerator due to finger tip impacts ranges from 0.9 V to 1.4V. Also for sensing application, the maximum output voltage response of the nanogenerator is found to be 2.86V due to stainless steel (SS) ball impact and 0.92 V due to plastic ball impact.

Identification of source of heavy metal contamination in a site - a case study

Accidental spills and improper disposal of industrial effluent/sludge containing heavy metals onto the open land or into subsurface result in soil and water contamination. Detailed investigations are carried out to identify the source of contamination of heavy metals in an industrial suburb near Bangalore in India. Detailed investigation of ground water and subsurface soil analysis for various heavy metals has been carried out. Ground water samples were collected in the entire area through the cluster of borewells. Subsurface soil samples were collected from near borewells which were found to contain heavy metals. Water samples and soils samples (after acid digestion) were analysed as per APHO-standard method of analysis. While the results of Zn, Ni and Cd showed that they are within allowable limits in the soil, the ground water and soils in the site have concentration of Cr+6 far exceeding the allowable limits (up to 832 mg/kg). Considering the topography of the area, ground water movement and results of chromium concentration in the borewells and subsurface it was possible to identify the origin, zone of contamination and the migration path of Cr+6. The results indicated that the predominant mechanism of migration of Cr+6 is by diffusion.

Ratiometric, reversible, and parts per billion level detection of multiple toxic transition metal ions using a single probe in micellar media

We present the selective sensing of multiple transition metal ions in water using a synthetic single probe. The probe is made up of pyrene and pyridine as signaling and interacting moiety, respectively. The sensor showed different responses toward metal ions just by varying the medium of detection. In organic solvent (acetonitrile), the probe showed selective detection of Hg2+ ion. In water, the fluorescence quenching was observed with three metal ions, Cu2+, Hg2+, and Ni2+. Further, just by varying the surface charge on the micellar aggregates, the probe could detect and discriminate the above-mentioned three different toxic metal ions appropriately. In neutral micelles (Brij 58), the probe showed a selective interaction with Hg2+ ion as observed in acetonitrile medium. However, in anionic micellar medium (sodium dodecyl sulfate, SDS), the probe showed changes with both Cu2+ and Ni2+. under UV-vis absorption spectroscopy. The discrimination between these two ions was achieved by recording their emission spectra, where it showed selective quenching with Cu2+.

Mechanical properties of a metal-organic framework containing hydrogen-bonded bifluoride linkers

We report the mechanical properties of a framework structure, Cu2F(HF)(HF2)(pyz)(4)](SbF6)(2)](n) (pyz = pyrazine), in which Cu(pyz)(2)](2+) layers are pillared by HF2- anions containing the exceptionally strong F-H center dot center dot center dot F hydrogen bonds. Nanoindentation studies on single-crystals clearly demonstrate that such bonds are extremely robust and mechanically comparable with coordination bonds in this system.

Performance limits of transition metal dichalcogenide (MX2) nanotube surround gate ballistic field effect transistors

We theoretically analyze the performance of transition metal dichalcogenide (MX2) single wall nanotube (SWNT) surround gate MOSFET, in the 10 nm technology node. We consider semiconducting armchair (n, n) SWNT of MoS2, MoSe2, WS2, and WSe2 for our study. The material properties of the nanotubes are evaluated from the density functional theory, and the ballistic device characteristics are obtained by self-consistently solving the Poisson-Schrodinger equation under the non-equilibrium Green's function formalism. Simulated ON currents are in the range of 61-76 mu A for 4.5 nm diameter MX2 tubes, with peak transconductance similar to 175-218 mu S and ON/OFF ratio similar to 0.6 x 10(5)-0.8 x 10(5). The subthreshold slope is similar to 62.22 mV/decade and a nominal drain induced barrier lowering of similar to 12-15 mV/V is observed for the devices. The tungsten dichalcogenide nanotubes offer superior device output characteristics compared to the molybdenum dichalcogenide nanotubes, with WSe2 showing the best performance. Studying SWNT diameters of 2.5-5 nm, it is found that increase in diameter provides smaller carrier effective mass and 4%-6% higher ON currents. Using mean free path calculation to project the quasi-ballistic currents, 62%-75% reduction from ballistic values in drain current in long channel lengths of 100, 200 nm is observed.

Performance and reliability of Gd2O3 and stacked Gd2O3-Eu2O3 metal-insulator-metal capacitors

Gd2O3-based metal-insulator-metal capacitors have been characterized with single layer (Gd2O3) and bilayer (Gd2O3/Eu2O3 and Eu2O3/Gd2O3) stacks for analog and DRAM applications. Although single layer Gd2O3 capacitors provide highest capacitance density (15 fF/mu m(2)), they suffer from high leakage current density, poor capacitance density-voltage linearity, and reliability. The stacked dielectrics help to reduce leakage current density (1.2x10(-5) A/cm(2) and 2.7 x 10(-5) A/cm(2) for Gd2O3/Eu2O3 and Eu2O3/Gd2O3, respectively, at -1 V), improve quadratic voltage coefficient of capacitance (331 ppm/V-2 and 374 ppm/V-2 for Gd2O3/Eu2O3 and Eu2O3/Gd2O3, respectively, at 1 MHz), and improve reliability, with a marginal reduction in capacitance density. This is attributed to lower trap heights as determined from Poole-Frenkel conduction mechanism, and lower defect density as determined from electrode polarization model.

Exploring the color of transition metal ions in irregular coordination geometries: new colored inorganic oxides based on the spiroffite structure, Zn2-xMxTe3O8 (M = Co, Ni, Cu)

We describe the synthesis, crystal structures, and optical absorption spectra of transition metal substituted spiroffite derivatives, Zn2-xMxTe3O8 (M-II = Co, Ni, Cu; 0 < x <= 1.0). The oxides are readily synthesized by solid state reaction of stoichiometric mixtures of the constituent binaries at 620 degrees C. Reitveld refinement of the crystal structures from powder X-ray diffraction (XRD) data shows that the Zn/MO6 octahedra are strongly distorted, as in the parent Zn2Te3O8 structure, consisting of five relatively short Zn/M-II-O bonds (1.898-2.236 angstrom) and one longer Zn/M-II-O bond (2.356-2.519 angstrom). We have interpreted the unique colors and the optical absorption/diffuse reflectance spectra of Zn2-xMxTe3O8 in the visible, in terms of the observed/irregular coordination geometry of the Zn/M-II-O chromophores. We could not however prepare the fully substituted M2Te3O8 (M-II = Co, Ni, Cu) by the direct solid state reaction method. Density Functional Theory (DFT) modeling of the electronic structure of both the parent and the transition metal substituted derivatives provides new insights into the bonding and the role of transition metals toward the origin of color in these materials. We believe that transition metal substituted spiroffites Zn2-xMxTe3O8 reported here suggest new directions for the development of colored inorganic materials/pigments featuring irregular/distorted oxygen coordination polyhedra around transition metal ions.

Selenium adsorption on Au(111) and Ag(111) surfaces: adsorbed selenium and selenide films

Results of a high resolution photoemission and electrochemistry study of Se adsorption Au(111) and Ag(111) surfaces performed by immersion of pristine samples into an aqeuous solution of Na2Se are presented. Cyclic voltammetry on Au shows formation of selenium adsorbed species and the structures observed in reductive desorption are to the atomic and polymeric species observed in XPS. In the case of Au(111) XPS spectra in the Se(3d) region indeed show two main features attributed to Se chemisorbed atomically and polymeric Se-8 features.' Smaller structures due to other types of Se conformations were also observed. The Au(4f) peak line, shape does not show core level, shifts: indicative of Au selenide formation the case of silver, XPS spectra for the Ag(3d) show a broadening of the peak and a deconvolution into Ag-B bulk like Ag-Se components shows that the Ag-Se is located at a lower binding energy, an effect similar to oxidation and sulfidation of Ag. The Se(3d) XPS spectrum is found to be substantially different from the Au case and dominated by atomic type Se due to the selenide, though a smaller intensity Se structure at an energy similar to the Se-8 structure for Au is also observed. Changes in the valence band region. related to Se adsorption are reported.

Calibration of etched fiber bragg grating sensor arrays for measurement of molecular surface adsorption

Etched Fiber Bragg Grating (EFBG) sensors are attractive from the point of the inherently high multiplexing ability of fiber based sensors. However, the strong dependence of the sensitivity of EFBG sensors on the fiber diameter requires robust methods for calibration when used for distributed sensing in a large array format. Using experimental data and numerical modelling, we show that knowledge of the wavelength shift during the etch process is necessary for high-fidelity calibration of EFBG arrays. However as this approach requires the monitoring of every element of the sensor array during etching, we also proposed and demonstrated a calibration scheme using data from bulk refractometry measurements conducted post-fabrication without needing any information about the etching process. Although this approach is not as precise as the first one, it may be more practical as there is no requirement to monitor each element of the sensor array. We were able to calibrate the response of the sensors to within 3% with the approach using information acquired during etching and to within 5% using the post-fabrication bulk refractometry approach in spite of the sensitivities of the array element differing by more than a factor of 4. These two approaches present a tradeoff between accuracy and practicality.

Metal doped nanosized titania used for the photocatalytic degradation of rhodamine B dye under visible-light

Metal-doped anatase nanosized titania photocatalysts were successfully synthesized using a sal gel process. Different amounts of the dopants (0.2, 0.4, 0.6, 0.8 and 1.0%) of the metals (Ag, Ni, Co and Pd) were utilized. The UV-Vis spectra (solid state diffuse reflectance spectra) of the doped nanoparticles exhibited a red shift in the absorption edge as a result of metal doping. The metal-doped nanoparticles were investigated for their photocatalytic activity under visible-light irradiation using Rhodamine B (Rh B) as a control pollutant. The results obtained indicate that the metal-doped titania had the highest activity at 0.4% metal loading. The kinetic models revealed that the photodegradation of Rh B followed a pseudo first order reaction. From ion chromatography (IC) analysis the degradation by-products Rhodamine B fragments were found to be acetate, chloride, nitrite, carbonate and nitrate ions.

DRIFTS studies on CO and NO adsorption and NO plus CO reaction over Pd2+-substituted CeO2 and Ce0.75Sn0.25O2 catalysts

Sequential adsorption of CO and NO as well as equimolar NO + CO reaction with variation of temperature over Pd2+ ion-substituted CeO2 and Ce0.75Sn0.25O2 supports has been studied by DRIFTS technique. The results are compared with 2 at.% Pd/Al2O3 containing Pd-0. Both linear and bridging Pd-0-CO bands are observed over 2 at.% Pd/Al2O3. But, band positions are shifted to higher frequencies in Ce0.98Pd0.02O2-delta and Ce0.73Sn0.25Pd0.02O2-delta catalysts that could be associated with Pd delta+-CO species. In contrast, a Pd2+-CO band at 2160 cm(-1) is observed upon CO adsorption over Ce0.98Pd0.02O2-delta and Ce0.73Sn0.25Pd0.02O2-delta catalysts pre-adsorbed with NO and a Pd+-CO band at 2120 cm(-1) is slowly developed on Ce(0.73)Srl(0.25)Pd(0.02)O(2-delta) over time. An intense linear Pd-0-NO band at 1750 cm(-1) found upon NO exposure to CO pre-adsorbed 2 at.% Pd/Al2O3 indicates molecular adsorption of NO. On the other hand, a weak Pd2+-NO band at 1850 cm(-1) is noticed after NO exposure to Ce0.98Pd0.02O2-delta catalyst pre-adsorbed with CO indicating dissociative adsorption of NO which is crucial for NO reduction. Pd-0-NO band is initially formed over CO pre-adsorbed Ce0.73Sn0.25Pd0.02O2-delta which is red-shifted over time along with formation of Pd2+-NO band. Several intense bands related to nitrates and nitrites are observed after exposure of NO to fresh as well as CO pre-adsorbed Ce0.98Pd0.02O2-delta and Ce0.73Sn0.25Pd0.02O2-delta catalysts. Ramping the temperature in a DRIFTS cell upon NO and CO adsorption shows the formation of N2O and NCO surface species, and N2O-formation temperature is comparable with the reaction done in a reactor.

Hydrodynamic energy harvesting using an ionic polymer-metal composite stack for underwater applications

Ionic Polymer Metal Composites (IPMCs) are a class of Electro-Active Polymers (EAPs) consisting of a base polymer (usually Nafion), sandwiched between thin films of electrodes and an electrolyte. Apart from fuel cell like proton exchange process in Nafion, these IPMCs can act both as an actuator and a sensor. Typically, IPMCs have been known for their applications in fuel cell technology and in artificial muscles for robots. However, more recently, sensing properties of IPMC have opened up possibilities of mechanical energy harvesting. In this paper, we consider a bi-layer stack of IPMC membranes where fluid flow induced cyclic oscillation allows collection of electronic charge across a pair of functionalized electrode on the surface of IPMC layers/stacks. IPMCs work well in hydrated environment; more specifically, in presence of an electrolyte, and therefore, have great potential in underwater applications like hydrodynamic energy harvesting. Hydrodynamic forces produce bending deformation, which can induce transport of cations via polymer chains of the base polymer of Nafion or PTFE. In our experimental set-up, the deformation is induced into the array of IPMC membranes immersed in electrolyte by water waves caused by a plunger connected to a stepper motor. The frequency and amplitude of the water waves is controlled by the stepper motor through a micro-controller. The generated electric power is measured across a resistive load. Few orders of magnitude increase in the harvested power density is observed. Analytical modeling approach used for power and efficiency calculations are discussed. The observed electro-mechanical performance promises a host of underwater energy harvesting applications.

Stabilization of diborane(4) by transition metal fragments and a novel metal to pi Dewar-Chatt-Duncanson model of back donation

The feasibility of using transition metal fragments to stabilize B2H4 in planar configuration by donating 2 electrons to the boron moiety is investigated. Building upon the existing theoretical and experimental data and aided by the isolobal analogy, the model transition metal complexes Cr(CO)(4)B2H4 (6), Mn(CO)-CpB2H4 (7), Fe(CO)(3)B2H4 (8) and CoCpB2H4 (9) are chosen to illustrate this unique bonding feature bond strengthening with pi-back donation. Other possible types of complexes with B2H4 and the metal fragment are also explored and the energies are compared. One of the low energy isomers wherein the planar B2H4 interacts with the metal fragment in an in-plane fashion represents a unique case study for the Dewar-Chatt-Duncanson model. In this complex the back-donation from the metal fills the p bonding orbital between the two boron atoms thus forming a B=B double bond.

Photoelectron spectromicroscopy study of metal-insulator transition in NaxWO3

We have investigated the validity of percolation model, which is quite often invoked to explain the metal-insulator transition in sodium tungsten bronzes, NaxWO(3) by photoelectron spectromicroscopy. The spatially resolved direct spectromicroscopic probing on both the insulating and metallic phases of high quality single crystals of NaxWO(3) reveals the absence of any microscopic inhomogeneities embedded in the system within the experimental limit. Neither any metallic domains in the insulating host nor any insulating domains in the metallic host have been found to support the validity of percolation model to explain the metal-insulator transition in NaxWO(3). The possible origin of insulating phase in NaxWO(3) is due to the Anderson localization of all the states near E-F. The localization occurs because of the strong disorder arising from random distribution of Na+ ions in the WO3 lattice.

Analysis of size quantization and temperature effects on the threshold voltage of thin silicon film double-gate metal-oxide-semiconductor field-effect transistor (MOSFET)

In this paper, we analyze the combined effects of size quantization and device temperature variations (T = 50K to 400 K) on the intrinsic carrier concentration (n(i)), electron concentration (n) and thereby on the threshold voltage (V-th) for thin silicon film (t(si) = 1 nm to 10 nm) based fully-depleted Double-Gate Silicon-on-Insulator MOSFETs. The threshold voltage (V-th) is defined as the gate voltage (V-g) at which the potential at the center of the channel (Phi(c)) begins to saturate (Phi(c) = Phi(c(sat))). It is shown that in the strong quantum confinement regime (t(si) <= 3nm), the effects of size quantization far over-ride the effects of temperature variations on the total change in band-gap (Delta E-g(eff)), intrinsic carrier concentration (n(i)), electron concentration (n), Phi(c(sat)) and the threshold voltage (V-th). On the other hand, for t(si) >= 4 nm, it is shown that size quantization effects recede with increasing t(si), while the effects of temperature variations become increasingly significant. Through detailed analysis, a physical model for the threshold voltage is presented both for the undoped and doped cases valid over a wide-range of device temperatures, silicon film thicknesses and substrate doping densities. Both in the undoped and doped cases, it is shown that the threshold voltage strongly depends on the channel charge density and that it is independent of incomplete ionization effects, at lower device temperatures. The results are compared with the published work available in literature, and it is shown that the present approach incorporates quantization and temperature effects over the entire temperature range. We also present an analytical model for V-th as a function of device temperature (T). (C) 2013 AIP Publishing LLC.