Diffusion pattern in MSi2 and M5Si3 silicides in group VB (M = V, Nb, Ta) and VIB (M = Mo, W) refractory metal-silicon systems

Group VB and VIB M-Si systems are considered to show an interesting pattern in the diffusion of components with the change in atomic number in a particular group (M = V, Nb, Ta or M = Mo, W, respectively). Mainly two phases, MSi2 and M5Si3 are considered for this discussion. Except for Ta-silicides, the activation energy for the integrated diffusion of MSi2 is always lower than M5Si3. In both phases, the relative mobilities measured by the ratio of the tracer diffusion coefficients, , decrease with an increasing atomic number in the given group. If determined at the same homologous temperature, the interdiffusion coefficients increase with the atomic number of the refractory metal in the MSi2 phases and decrease in the M5Si3 ones. This behaviour features the basic changes in the defect concentrations on different sublattices with a change in the atomic number of the refractory components.

Electronic band Structure and Photoemission Spectra of Graphene on Silicon Substrate

Synergizing graphene on silicon based nanostructures is pivotal in advancing nano-electronic device technology. A combination of molecular dynamics and density functional theory has been used to predict the electronic energy band structure and photo-emission spectrum for graphene-Si system with silicon as a substrate for graphene. The equilibrium geometry of the system after energy minimization is obtained from molecular dynamics simulations. For the stable geometry obtained, density functional theory calculations are employed to determine the energy band structure and dielectric constant of the system. Further the work function of the system which is a direct consequence of photoemission spectrum is calculated from the energy band structure using random phase approximations.

Spontaneous Breaking of Time-Reversal Symmetry in Strongly Interacting Two-Dimensional Electron Layers in Silicon and Germanium

We report experimental evidence of a remarkable spontaneous time-reversal symmetry breaking in two-dimensional electron systems formed by atomically confined doping of phosphorus (P) atoms inside bulk crystalline silicon (Si) and germanium (Ge). Weak localization corrections to the conductivity and the universal conductance fluctuations were both found to decrease rapidly with decreasing doping in the Si: P and Ge: P delta layers, suggesting an effect driven by Coulomb interactions. In-plane magnetotransport measurements indicate the presence of intrinsic local spin fluctuations at low doping, providing a microscopic mechanism for spontaneous lifting of the time-reversal symmetry. Our experiments suggest the emergence of a new many-body quantum state when two-dimensional electrons are confined to narrow half-filled impurity bands.

Pressure-induced semiconducting to metallic transition in multilayered molybdenum disulphide

Molybdenum disulphide is a layered transition metal dichalcogenide that has recently raised considerable interest due to its unique semiconducting and opto-electronic properties. Although several theoretical studies have suggested an electronic phase transition in molybdenum disulphide, there has been a lack of experimental evidence. Here we report comprehensive studies on the pressure-dependent electronic, vibrational, optical and structural properties of multilayered molybdenum disulphide up to 35 GPa. Our experimental results reveal a structural lattice distortion followed by an electronic transition from a semiconducting to metallic state at similar to 19 GPa, which is confirmed by ab initio calculations. The metallization arises from the overlap of the valance and conduction bands owing to sulphur-sulphur interactions as the interlayer spacing reduces. The electronic transition affords modulation of the opto-electronic gain in molybdenum disulphide. This pressure-tuned behaviour can enable the development of novel devices with multiple phenomena involving the strong coupling of the mechanical, electrical and optical properties of layered nanomaterials.

Conducting polymer-carbon black nanocomposite sensor for volatile organic compounds and correlating sensor response by molecular dynamics

Volatile organic compounds (VOCs) are present in our every day used products such as plastics, cosmetics, air fresheners, paint, etc. The determination of amount of VOC present in atmosphere can be carried out via various sensors. In this work a nanocomposite of a novel thiophene based conducting polymer and carbon black is used as a volatile organic compound sensor. The fabricated 2 lead chemiresistor sensor was tested for vapours of toluene, acetone, cylcohexane, and carbon tetrachloride. The sensor responds to all the vapours, however, exhibit maximum response to toluene vapours. The sensor was evaluated for various concentrations of toluene. The lower limit of detection of the sensor is 15 +/- 10 ppm. The study of the effect of humidity on senor response to toluene showed that the response decreases at higher humidity conditions. The surface morphology of the nanocomposite was characterized by scanning electron microscopy. Diffuse reflectance spectroscopy was used to investigate the absorption of vapours by the nanocomposite film. Contact angle measurements were used to present the effect of water vapour on the toluene response of nanocomposite film. Solubility parameter of the conducting polymer is predicted by molecular dynamics. The sensing behaviour of the conducting polymer is correlated with solubility parameter of the polymer. Dispersion interaction of conducting polymer with toluene is believed to be the reason for the selective response towards toluene. (C) 2014 Elsevier B.V. All rights reserved.

Fabrication and characterization of gold coated hollow silicon microneedle array for drug delivery

In this paper, we present the fabrication and characterization of Ti and Au coated hollow silicon microneedles for transdermal drug delivery applications. The hollow silicon microneedles are fabricated using isotropic etching followed by anisotropic etching to obtain a tapered tip. Silicon microneedle of 300 mu m in height, with 130 mu m outer diameter and 110 mu m inner diameter at the tip followed by 80 mu m inner diameter and 160 mu m outer diameter at the base have been fabricated. In order to improve the biocompatibility of microneedles, the fabricated microneedles were coated with Ti (500 nm) by sputtering technique followed by gold coating using electroplating. A breaking force of 225 N was obtained for the fabricated microneedles, which is 10 times higher than the skin resistive force. Hence, fabricated microneedles can easily be inserted inside the skin without breakage. The fluid flow through the microneedles was studied for different inlet pressures. A minimum inlet pressure of 0.66 kPa was required to achieve a flow rate of 50 mu l in 2 s with de-ionized water as a fluid medium. (C) 2014 Elsevier B.V. All rights reserved.

A framework for post-silicon realization of arbitrary instruction extensions on reconfigurable data-paths

In this paper we present a framework for realizing arbitrary instruction set extensions (IE) that are identified post-silicon. The proposed framework has two components viz., an IE synthesis methodology and the architecture of a reconfigurable data-path for realization of the such IEs. The IE synthesis methodology ensures maximal utilization of resources on the reconfigurable data-path. In this context we present the techniques used to realize IEs for applications that demand high throughput or those that must process data streams. The reconfigurable hardware called HyperCell comprises a reconfigurable execution fabric. The fabric is a collection of interconnected compute units. A typical use case of HyperCell is where it acts as a co-processor with a host and accelerates execution of IEs that are defined post-silicon. We demonstrate the effectiveness of our approach by evaluating the performance of some well-known integer kernels that are realized as IEs on HyperCell. Our methodology for realizing IEs through HyperCells permits overlapping of potentially all memory transactions with computations. We show significant improvement in performance for streaming applications over general purpose processor based solutions, by fully pipelining the data-path. (C) 2014 Elsevier B.V. All rights reserved.

Hetero-tri-spin 2p-3d-4f] Chain Compounds Based on Nitronyl Nitroxide Lanthanide Metallo-Ligands: Synthesis, Structure, and Magnetic Properties

Employing nitronyl nitroxide lanthanide(III) complexes as metallo-ligands allowed the efficient and highly selective preparation of three series of unprecedented heterotri-spin (Cu Ln-radical) one-dimensional compounds. These 2p-3d-4f spin systems, namely Ln(3)Cu(hfac)II(NitPhOAII)41 (Ln(III)=Gd 1(Gd), Tb 1(Tb), Dy 1(Dy); NitPhOAII=2-(4'-allyloxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3- oxide), Ln(3)Cu(hfac)II(NitPhOPO4] (1-nrn=Gd 2Gd, Tb 2Tb, Dy 2(Dy), Ho 2HOf Yb 2yb; NitPhOPr= 2-(4'-propoxyphenyI)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) and Ln3Cu(hfac)II(NitPhOB441 (LnIm=Gd 3Gd, Tb 3Tb, Dy 3(Dy); NitPhOBz=2-(4'-benzyloxy- phenyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) involve O-bound nitronyl nitroxide radicals as bridging ligands in chain structures with a Cu-Nit-Ln-Nit-Ln-Nit-Ln-Nit] repeating unit. The dc magnetic studies show that ferromagnetic metal radical interactions take place in these heterotri-spin chain complexes, these and the next-neighbor interactions have been quantified for the Gd derivatives. Complexes 1Tb and 2Tb exhibit frequency dependence of ac magnetic susceptibilities, indicating single-chain magnet behavior.

On the quality of hydrogenated amorphous silicon deposited by sputtering

Amorphous hydrogenated silicon (a-Si:H) is well-known material in the global semiconductor industry. The quality of the a-Si:H films is generally decided by silicon and hydrogen bonding configuration (Si-H-x, x=1,2) and hydrogen concentration (C-H). These quality aspects are correlated with the plasma parameters like ion density (N-i) and electron temperature (T-e) of DC, Pulsed DC (PDC) and RF plasmas during the sputter-deposition of a-Si:H thin films. It was found that the N-i and T-e play a major role in deciding Si-H-x bonding configuration and the C-H value in a-Si:H films. We observed a trend in the variation of Si-H and Si-H-2 bonding configurations, and C-H in the films deposited by DC, Pulsed DC and RF reactive sputtering techniques. Ion density and electron energy are higher in RF plasma followed by PDC and DC plasma. Electrons with two different energies were observed in all the plasmas. At a particular hydrogen partial pressure, RF deposited films have higher C-H followed by PDC and then DC deposited films. The maximum energy that can be acquired by the ions was found to be higher in RF plasma. Floating potential (V-f) is more negative in DC plasma, whereas, plasma potential (V-p) is found to be more positive in RF plasma. (C) 2014 Elsevier Ltd. All rights reserved.

Surface modification of textured silicon and its wetting behaviour

Textured silicon (Si) substrate were prepared using various texturing methods both chemical and physical and their water contact angle, surface topography and Raman spectra were studied and investigated. The effect of plasma and chemical treatment on micro/nanostructure and roughness of the surface with and without deposition of Octadecyltrichlorosilane (ODTS, Cl3Si (CH3)(17)), self-assembled monolayer (SAM) is investigated for achieving higher water contact angle (theta(c)). The importance of synergism of texturing with deposition of ODTS SAM in preparing superhydrophobic silicon surfaces has been discussed. It is shown that superhydrophobic silicon surfaces can be achieved on silicon surfaces by coating with ODTS, irrespective of whether it is textured or not, polished or unpolished, provided a chemical treatment is given to the surface prior to the ODTS coating.

Structural, magnetic and electrochemical investigation of novel binary Na2-x(Fe1-yMny)P2O7 (0 <= y <= 1) pyrophosphate compounds for rechargeable sodium-ion batteries

Pyrophosphate cathodes have been recently reported as a competent family of insertion compounds for sodium-ion batteries. In the current study, we have investigated the binary Na2 - x(Fe1 - yMny)P2O7 (0 <= y <= 1) pyrophosphate family, synthesized by the classical solid-state method. They form a continuous solid solution maintaining triclinic P-1 (#2) symmetry. The local structural coordination differs mainly by different degrees of Na site occupancy and preferential occupation of the Fe2 site by Mn. The structural and magnetic properties of these mixed-metal pyrophosphate phases have been studied. In each case, complete Fe3+/Fe2+ redox activity has been obtained centered at 3 V vs. Na. The Fe3+/Fe2+ redox process involves multiple steps between 2.5 and 3 V owing to Na-cation ordering during electrochemical cycling, which merge to form a broad single Fe3+/Fe2+ redox peak upon progressive Mn-doping. (C) 2014 Elsevier B.V. All rights reserved.

Silicon isotopes: from cosmos to benthos

Silicon is the second most abundant element on the Earth and one of the more abundant elements in our Solar System. Variations in the relative abundance of the stable isotopes of Si (Si isotope fractionation) in different natural reservoirs, both terrestrial (surface and deep Earth) as well as extra-terrestrial (e.g. meteorites, lunar samples), are a powerful tracer of present and past processes involving abiotic as well as biotic systems. The versatility of the Si isotope tracer is reflected in its wide-ranging applications from understanding the origin of early Solar System objects, planetary differentiation, Moon formation, mantle melting and magma differentiation on the Earth, ancient sea-water composition, to modern-day weathering, clay formation and biological fractionation on land as well as in the oceans. The application of Si isotopes as tracers of natural processes started over six decades ago and its usage has seen a sudden increase over the last decade due to improvements in mass spectrometry, particularly the advent of multi-collector inductively coupled plasma mass spectrometers, which has made Si isotope measurements safe and relatively easy while simultaneously improving the accuracy and precision of measurements.

High Proton Mobility, Solvent Induced Single Crystal to Single Crystal Structural Transformation, and Related Studies on a Family of Compounds Formed from Mn-3 Oxo-Clusters

The reaction between 4,4'-sulfonyldibenzoic acid (H(2)SDBA) and manganese under mild conditions resulted in the isolation of two new three-dimensional compounds, Mn-4(C14H8O6S)(4)(DMA)(2)]center dot 3DMA, I, and Mn-3(C14H8O6S)(3)(DMA)(2)(MeOH)]center dot DMA, IIa. Both structures have Mn-3 trimer oxo cluster units. While the Mn-3 oxoclusters are connected through octahedral manganese forming one-dimensional Mn-O-Mn chains in I, the Mn-3 units are isolated in IIa. The SDBA units connect the Mn-O-Mn chains and the Mn-3 clusters giving rise to the three-dimensional structure. Both compounds have coordinated and free solvent molecules. In IIa, two different solvent molecules are coordinated, of which one solvent can be reversibly exchanged by a variety of other similar solvents via a solvent-mediated single crystal to single crystal (SCSC) transformation. The free lattice DMA solvent molecules in I can be exchanged by water molecules resulting in hydrophilic channels. Proton conductivity studies on I reveals a high proton mobility with conductivity values of similar to 0.87 x 10(-3) Omega(-1) cm(-1) at 34 degrees C and 98% RH, which is comparable to some of the good proton conductivity values observed in inorganic coordination polymers. We have also shown structural transformation of I to IIa through a possible dissolution and recrystallization pathway. In addition, both I and IIa appear to transform to two other manganese compounds H3O]Mn-3(mu(3)-OH)(C14H8O6S)(3)(H2O)](DMF)(5) and H3O](2)Mn-7(mu 3-OH)(4)(C14H8O6S)(6)(H2O)(4)](H2O)(2)(DMF)(8) under suitable reaction conditions. We have partially substituted Co in place of Mn in the Mn-3 trimer clusters forming CoMn2(C14H8O6S)(3)(DMA)(2)(EtOH)]center dot DMA, III, a structure that is closely related to IIa. All the compounds reveal antiferromagnetic behavior. On heating, the cobalt substituted phase (compound III) forms a CoMn2O4 spinel phase with particle sizes in the nanometer range.

Effect of lateral substituent and chain length on mesomorphic properties of novel alkoxy benzyloxy benzoates of cyanophenyl rod-shaped compounds

Three novel homologous series of rod-shaped cyanophenyl alkoxy benzoate liquid crystalline compounds with lateral polar fluorine and chlorine substituent were prepared, and chemical structures of novel materials have been characterized by standard spectral technique and elemental analysis. The mesophase characterization was carried out using the combination of polarized optical microscopy and differential scanning calorimetry. All the compounds exhibit wide thermal range of enantiotropic SmA phase.

A Mild Protocol for the Regioselective Ring Opening of Doubly Activated Cyclopropanes by Using Selenolates Generated in Situ: Synthesis of Functionalized Organoselenium Compounds

A variety of functionalized organoselenium compounds were synthesized from doubly activated cyclopropanes and diselenides in the presence of sodium borohydride. A range of substituents were stable under these reaction conditions. Additionally, we extended the scope of the method by reducing nitro groups in the products to give the corresponding selenium-containing unnatural amino acids.