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.

Clusters, asters, and collective oscillations in chemotactic colloids

The creation of synthetic systems that emulate the defining properties of living matter, such as motility, gradient-sensing, signaling, and replication, is a grand challenge of biomimetics. Such imitations of life crucially contain active components that transform chemical energy into directed motion. These artificial realizations of motility point in the direction of a new paradigm in engineering, through the design of emergent behavior by manipulating properties at the scale of the individual components. Catalytic colloidal swimmers are a particularly promising example of such systems. Here we present a comprehensive theoretical description of gradient-sensing of an individual swimmer, leading controllably to chemotactic or anti-chemotactic behavior, and use it to construct a framework for studying their collective behavior. We find that both the positional and the orientational degrees of freedom of the active colloids can exhibit condensation, signaling formation of clusters and asters. The kinetics of catalysis introduces a natural control parameter for the range of the interaction mediated by the diffusing chemical species. For various regimes in parameter space in the long-ranged limit our system displays precise analogs to gravitational collapse, plasma oscillations, and electrostatic screening. We present prescriptions for how to tune the surface properties of the colloids during fabrication to achieve each type of behavior.

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.

Cu-II-Azide Polynuclear Complexes of Three Different Building Clusters with the Same Schiff-Base Ligand: Synthesis, Structures, Magnetic Behavior, and Density Functional Theory Studies

Three copper-azido complexes Cu-4(N-3)(8)(L-1)(2)(MeOH)(2)](n) (1), Cu-4(N-3)(8)(L-1)(2)] (2), and Cu-5(N-3)(10)(L-1)(2)](n) (3) L-1 is the imine resulting from the condensation of pyridine-2-carboxaldehyde with 2-(2-pyridyl)ethylamine] have been synthesized using lower molar equivalents of the Schiff base ligand 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 the complexes 1 and 2 contains Cu-4(II) building blocks; however, they have distinct basic and overall structures due to a small change in the bridging mode of the peripheral pair of copper atoms in the linear tetranudear structures. Interestingly, these changes are the result of changing the solvent system (MeOH/H2O to EtOH/H2O) used for the synthesis, without changing the proportions of the components (metal to ligand ratio 2:1). Using even lower proportions of the ligand, another unique complex was isolated with Cu-5(II) building units, forming a two-dimensional complex (3). Magnetic susceptibility measurements over a wide range of temperature exhibit the presence of both antiferromagnetic (very weak) and ferromagnetic exchanges within the tetranuclear unit structures. Density functional theory calculations (using B3LYP functional, and two different basis sets) have been performed on the complexes 1 and 2 to provide a qualitative theoretical interpretation of their overall magnetic behavior.

Designing stuffed hetero-fullerene nano-clusters: C26B46N12 and C14B58N12Li12

The stuffed fullerene-like nano clusters based on the approximately spherical B-84, (B-12@B-12@B-60, fragment of the beta-rhombohedral boron), are proposed using Wade's Rules and the criterion of overlap matching. Thus the fifty additional electrons required to make the B-84 skeleton electron sufficient, are provided by replacing 26 boron atoms by carbon atoms and 12 boron atoms by nitrogen atoms giving rise to C26B46N12. This particular combination has the added advantage of the fullerene surface made from C2B3N five-membered rings having less strain arising from the pyramidalization of the sp(2) hybridised trigonal planar carbon or nitrogen; the natural angle needed to have an optimum overlap is not far from the 31.7 degrees required for icosahedral symmetry. The advantage from overlap-matching can be further increased by capping the two pentagonal faces of the cluster by a Li atom each, keeping the electron count the same by replacing 12 carbon atoms with 12 boron atoms. DFT based computational results support these formulations.

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.

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.

A Reactive Intermediate, Ni-5(C6H4N3)(6)(CO)(4)], in the Formation of Nonameric Clusters of Nickel, Ni-9(C6H4N3)(12)(CO)(6)] and Ni-9(C6H4N3)(12)(CO)(6)].2(C3H7NO)

Three new molecular compounds, Ni-5(bta)(6)(CO)(4)], I, Ni-9(bta)(12)(CO)(6)], II, Ni-9(bta)(12)(CO)(6)]. 2(C3H7NO), III, (bta = benzotriazole) were prepared employing solvothermal reactions. Of these, I have pentanuclear nickel, whereas II and III have nonanuclear nickel species. The structures are formed by the connectivity between the nickel and benzotriazole giving rise to the 5- and 9-membered nickel clusters. The structures are stabilised by extensive pi aEuro broken vertical bar pi and C-H... pi interactions. Compound II and III are solvotamorphs as they have the same 9-membered nickel clusters and have different solvent molecules. To the best of our knowledge, the compounds I-III represent the first examples of the same transition element existing in two distinct coordination environment in this class of compounds. The studies reveal that compound I is reactive and could be an intermediate in the preparation of II and III. Thermal studies indicate that the compounds are stable upto 350(a similar to)C and at higher temperatures (similar to 800(a similar to)C) the compounds decompose into NiO. Magnetic studies reveal that II is anti-ferromagnetic.

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.

Electronically nonadiabatic decomposition mechanisms of clusters of zinc and dimethylnitramine

Electronically nonadiabatic decomposition mechanisms of dimethylnitramine (DMNA) in presence of zinc metal clusters are explored. Complete active space self-consistent field (CASSCF) calculation is employed for DMNA-Zn and ONIOM (Our own N-layered integrated molecular orbital and molecular mechanics) methodology is coupled with CASSCF methodology for DMNA-Zn-10 cluster. Present computational results show that DMNA-Zn clusters undergo electronically nonadiabatic reactions, rendering nitro-nitrite isomerization followed by NO elimination. The overall reactions are also found to be highly exothermic in nature. This is the first report on electronically nonadiabatic decomposition pathways of DMNA-Zn-n neutral clusters. (C) 2014 Elsevier B.V. All rights reserved.

Remarkable enhancement in hydrogen storage on free-standing Ti3B and BC3 supported Ti-3 clusters

Hydrogen storage capacity of Tin-1B (n = 3-7) clusters is studied and compared with that of the pristine Ti-n (n = 3-7), using density functional theory (DFT) based calculations. Among these clusters, Ti3B shows the most significant enhancement in the storage capacity by adsorbing 12 H-2, out of which three are dissociated and the other nine are stored as dihydrogen via Kubas-interaction. The best storage in Ti3B is owed to a large charge transfer from Ti to B along with the largest distance of Ti empty d-states above the Fermi level, which is a distinct feature of this particular cluster. Furthermore, the effect of substrates on the storage capacity of Ti3B was assessed by calculating the number of adsorbed H-2 on Ti-3 cluster anchored onto B atoms in the B-doped graphene, BC3, and BN substrates. Similar to free-standing Ti3B, Ti-3 anchored onto boron atom in BC3, stores nine di-hydrogen via Kubas interaction, at the same time eliminating the total number of non-useful dissociated hydrogen. Gibbs energy of adsorption as a function of H-2 partial pressure, indicated that at 250 K and 300 K the di-hydrogens on Ti-3@BC3 adsorb and desorb at ambient pressures. Importantly, Ti-3@BC3 avoids the clustering, hence meeting the criteria for efficient and reversible hydrogen storage media. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. 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.