Observation of high pressure o-GeTe phase at ambient pressure in Si-Te-Ge glasses

Te-rich Si15Te85-xGex (1 <= x <= 11) glasses are found to exhibit an anomalous phase separations with germanium composition. The structural transformation of o-GeTe crystalline phase from o-GeTe with a = 11.76 angstrom, b = 16.59 angstrom, c = 17.44 angstrom, to high pressure o-GeTe with a new reduced lattice parameters a = 10.95 angstrom, b = 4.03 angstrom, c = 4.45 angstrom, is observed at T-c3 in the composition range 6 <= x <= 11. Raman studies support the possible existence of high pressure o-GeTe phase which is observed in X-ray diffraction experiments. Copyright 2012 Author(s). This article is distributed under a Creative Commons Attribution 3.0 Unported License. http://dx.doi.org/10.1063/1.3696862]

Carrier-transport studies of III-nitride/Si3N4/Si isotype heterojunctions

GaN/Si3N4/n-Si and InN/Si3N4/n-Si heterojunctions (HJs) were fabricated using plasma-assisted molecular beam epitaxy for a comparison study. Single-crystalline wurtzite structures of GaN and InN epilayers were confirmed by high-resolution X-ray diffraction and thickness of ultrathin Si3N4 layer was measured by transmission electron microscopy. n-GaN/Si3N4/n-Si HJs show diode-like rectifying current-voltage (I-V) characteristic, while n-InN/Si3N4/n-Si HJs show symmetric nonlinear I-V behavior. The I-V characteristics of both HJs were discussed in terms of the band diagram of HJs and the carrier transport mechanism. The activation energies of carrier conduction were estimated to be similar to 29 meV for GaN/Si3N4/Si and similar to 95 meV for InN/Si3N4/Si HJs. (C) 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Carrier concentration dependence of donor activation energy in n-type GaN epilayers grown on Si (111) by plasma-assisted MBE

The n-type GaN layers were grown by plasma-assisted MBE and either intentionally doped with Si or unintentionally doped. The optical characteristics of a donor level in Si-doped, GaN were studied in terms of photoluminescence (PL) spectroscopy as a function of electron concentration. Temperature dependent PL measurements allowed us to estimate the activation energy of a Si-related donor from temperature-induced decay of PL intensity. PL peak positions, full width at half maximum of PL and activation energies are found to be proportional to the cube root of carrier density. The involvement of donor levels is supported by the temperature-dependent electron concentration measurements. (C) 2012 Elsevier Ltd. All rights reserved.

Valence band offset at GaN/beta-Si3N4 and beta-Si3N4/Si(111) heterojunctions formed by plasma-assisted molecular beam epitaxy

Ultra thin films of pure beta-Si3N4 (0001) were grown on Si (111) surface by exposing the surface to radio- frequency nitrogen plasma with a high content of nitrogen atoms. Using beta-Si3N4 layer as a buffer layer, GaN epilayers were grown on Si (111) substrate by plasma-assisted molecular beam epitaxy. The valence band offset (VBO) of GaN/beta-Si3N4/ Si heterojunctions is determined by X-ray photoemission spectroscopy. The VBO at the beta-Si3N4 /Si interface was determined by valence-band photoelectron spectra to be 1.84 eV. The valence band of GaN is found to be 0.41 +/- 0.05 eV below that of beta-Si3N4 and a type-II heterojunction. The conduction band offset was deduced to be similar to 2.36 eV, and a change of the interface dipole of 1.29 eV was observed for GaN/ beta-Si3N4 interface formation. (c) 2011 Elsevier B.V. All rights reserved.

Study of n-ZnO/p-Si (100) thin film heterojunctions by pulsed laser deposition without buffer layer

ZnO/Si heterojunctions were fabricated by growing ZnO thin films on p-type Si (100) substrate by pulsed laser deposition without buffer layers. The crystallinity of the heterojunction was analyzed by high resolution X-ray diffraction and atomic force microscopy. The optical quality of the film was analyzed by room temperature (RT) photoluminescence measurements. The high intense band to band emission confirmed the high quality of the ZnO thin films on Si. The electrical properties of the junction were studied by temperature dependent current-voltage measurements and RT capacitance-voltage (C-V) analysis. The charge carrier concentration and the barrier height (BH) were calculated, to be 5.6x10(19) cm(-3) and 0.6 eV respectively from the C-V plot. The BH and ideality factor, calculated using the thermionic emission (TE) model, were found to be highly temperature dependent. We observed a much lower value in Richardson constant, 5.19x10(-7)A/cm(2) K-2 than the theoretical value (32 A/cm(2) K-2) for ZnO. This analysis revealed the existence of a Gaussian distribution (GD) with a standard deviation of sigma(2)=0.035 V. By implementing the GD to the TE, the values of BH and Richardson constant were obtained as 1.3 eV and 39.97 A/cm(2) K-2 respectively from the modified Richardson plot. The obtained Richardson constant value is close to the theoretical value for n-ZnO. These high quality heterojunctions can be used for solar cell applications. (C) 2012 Elsevier B.V. All rights reserved.

Si isotope variability in Proterozoic cherts

We report Si-isotopic compositions of 75 sedimentologically and petrographically characterized chert samples with ages ranging from similar to 2600 to 750 Ma using multi-collector inductively coupled plasma mass spectrometry. delta Si-30 values of the cherts analyzed in this study show a similar to 7 parts per thousand range, from -4.29 to +2.85. This variability can be explained in part by (1) simple mixing of silica derived from continental (higher delta Si-30) and hydrothermal (lower delta Si-30) sources, (2) multiple mechanisms of silica precipitation and (3) Rayleigh-type fractionations within pore waters of individual basins. We observe similar to 3 parts per thousand variation in peritidal cherts from a single Neoproterozoic sedimentary basin (Spitsbergen). This variation can be explained by Rayleigh-type fractionation during precipitation from silica-saturated porewaters. In some samples, post-dissolution and reprecipitation of silica could have added to this effect. Our data also indicate that peritidal cherts are enriched in the heavier isotopes of Si whereas basinal cherts associated with banded iron formations (BIF) show lower delta Si-30. This difference could partly be due to Si being derived from hydrothermal sources in BIFs. We postulate that the difference in delta Si-30 between non-BIF and BIF cherts is consistent with the contrasting genesis of these deposits. Low delta Si-30 in BIF is consistent with laboratory experiments showing that silica adsorbed onto Fe-hydroxide particles preferentially incorporates lighter Si isotopes. Despite large intrabasinal variation and environmental differences, the data show a clear pattern of secular variation. Low delta Si-30 in Archean cherts is consistent with a dominantly hydrothermal source of silica to the oceans at that time. The monotonically increasing delta Si-30 from 3.8 to 1.5 Ga appears to reflect a general increase in continental versus hydrothermal sources of Si in seawater, as well as the preferential removal of lighter Si isotopes during silica precipitation in iron-associated cherts from silica-saturated seawater. The highest delta Si-30 values are observed in 1.5 Ga peritidal cherts; in part, these enriched values could reflect increasing sequestration of light silica during soil-forming processes, thus, delivering relatively heavy dissolved silica to the oceans from continental sources. The causes behind the reversal in trend towards lower delta Si-30 in cherts younger than 1.5 Ga old are less clear. Cherts deposited 1800-1900 Ma are especially low delta Si-30, a possible indication of transiently strong hydrothermal input at this time. (C) 2012 Elsevier Ltd. All rights reserved.

Vapor-liquid-solid growth of Si nanowires: A kinetic analysis

A steady state kinetic model has been developed for the vapor-liquid-solid growth of Si whiskers or nanowires from liquid catalyst droplets. The steady state is defined as one in which the net injection rate of Si into the droplet is equal to the ejection rate due to wire growth. Expressions that represent specific mechanisms of injection and ejection of Si atoms from the liquid catalyst droplet have been used and their relative importance has been discussed. The analysis shows that evaporation and reverse reaction rates need to be invoked, apart from just surface cracking of the precursor, in order to make the growth rate radius dependent. When these pathways can be neglected, the growth rate become radius independent and can be used to determine the activation energies for the rate limiting step of heterogeneous precursor decomposition. The ejection rates depend on the mechanism of wire growth at the liquid-solid interface or the liquid-solid-vapor triple phase boundary. It is shown that when wire growth is by nucleation and motion of ledges, a radius dependence of growth rate does not just come from the Gibbs-Thompson effect on supersaturation in the liquid, but also from the dependence of the actual area or length available for nucleation. Growth rates have been calculated using the framework of equations developed and compared with experimental results. The agreement in trends is found to be excellent. The same framework of equations has also been used to account for the diverse pressure and temperature dependence of growth rates reported in the literature. © 2012 American Institute of Physics.

Electrical transport studies of MBE grown InGaN/Si isotype heterojunctions

The temperature dependent electrical transport behavior of n-n InGaN/Si heterostructures grown by plasma-assisted MBE was studied. Structural characteristics of the as-grown InGaN epilayers were evaluated high resolution X-ray diffraction and composition of InGaN was estimated from photoluminescence spectra using standard Vegard's law. Current density-voltage plots (J-V-T) revealed that the ideality factor (eta) and Schottky barrier height (SBH) (Phi(b)) are temperature dependent and the incorrect values of the Richardson's constant (A**) produced, suggests an inhomogeneous barrier at the heterostructure interface. The higher value of the ideality factor compared to the ideal value and its temperature dependence suggest that the current transport is mainly dominated by thermionic field emission. (C) 2012 Elsevier B.V. All rights reserved.

A Single-Stage Water-Gas Shift Reaction over Highly Active and Stable Si- and Al-Substituted Pt/CeO2 Catalysts

Ce0.88Si0.1Pt0.02O2-d and Ce0.88Al0.1Pt0.02O2-d catalysts were synthesized by using a low-temperature sonochemical method and characterized by using XRD, TEM, XPS, FTIR, and BET surface analyzer. The catalytic activities of these compounds were investigated for the watergas shift reaction in the temperature range of 140-440 degrees C. The substitution of Si in Ce0.98Pt0.02O2-d increased the releasing capacity of lattice oxygen, whereas the substitution of Al decreased the reducibility of Ce0.98Pt0.02O2-d, as evidenced by hydrogen temperature-programmed reduction studies. However, both the catalysts showed a considerable improvement in terms of activity and stability compared to Ce0.98Pt0.02O2-d. The combined activity measurement and characterization results suggest that the increase in the oxygen vacancy, which acts as a dissociation center for water, is the primary reason for the improvement in the activity of modified Ce0.98Pt0.02O2-d. Both the catalysts are 100?% selective toward H2 production, and approximately 99?% conversion of CO to CO2 was observed at 260 and 270 degrees C for Ce0.88Si0.1Pt0.02O2-d and Ce0.88Al0.1Pt0.02O2-d, respectively. These catalysts do not deactivate during the daily startup/shutdown operations and are sustainable even after prolonged reaction. Notably, these catalysts do not require any pretreatment or activation during startup/shutdown operations.

Effect of pouring temperature on cooling slope casting of semi-solid Al-Si-Mg alloy

Present trend of semi-solid processing is directed towards rheocasting route which allows manufacturing of near-net-shape cast components directly from the prepared semi-solid slurry. Generation of globular equi-axed grains during solidification of rheocast components, compared to the columnar dendritic structure of conventional casting routes, facilitates the manufacturing of components with improved mechanical properties and structural integrity. In the present investigation, a cooling slope has been designed and indigenously fabricated to produce semi solid slurry of Al-Si-Mg (A356) alloy and successively cast in a metallic mould. The scope of the present work discusses about development of a numerical model to simulate the liquid metal flow through cooling slope using Eulerian two-phase flow approach and to investigate the effect of pouring temperature on cooling slope semi-solid slurry generation process. The two phases considered in the present model are liquid metal and air. Solid fraction evolution of the solidifying melt is tracked at different locations of the cooling slope, following Schiel's equation. The continuity equation, momentum equation and energy equation are solved considering thin wall boundary condition approach. During solidification of the liquid metal, a modified temperature recovery scheme has been employed taking care of the latent heat release and change of fraction of liquid. The results obtained from simulations are compared with experimental findings and good agreement has been found.

Stress and texture development during sputtering of yttria, zirconia, and yttria stabilized zirconia films on Si substrates

Understanding and controlling growth stress is a requisite for integrating oxides with Si. Yttria stabilized zirconia (YSZ) is both an important functional oxide and a buffer layer material needed for integrating other functional oxides. Stress evolution during the growth of (100) and (111) oriented YSZ on Si (100) by radio frequency and reactive direct current sputtering has been investigated with an in-situ monitor and correlated with texture evolution. Films nucleated at rates <5 nm/min are found to be (111) oriented and grow predominantly under a compressive steady state stress. Films nucleated at rates >20 nm/min are found to be (100) oriented and grow under tension. A change in growth rate following the nucleation stage does not change the orientation. The value of the final steady state stress varies from -4.7 GPa to 0.3 GPa. The in-situ studies show that the steady state stress generation is a dynamic phenomenon occurring at the growth surface and not decided at film nucleation. The combination of stress evolution and texture evolution data shows that the adatom injection into the grain boundaries is the predominant source of compressive stress and grain boundary formation at the growth surface is the source of tensile stress. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4757924]

Relation between the work function and Young's modulus of RhSi and estimate of Schottky-barrier height at RhSi/Si interface: An ab-initio study

Density-functional calculations are performed to explore the relationship between the work function and Young's modulus of RhSi, and to estimate the p-Schottky-barrier height (SBH) at the Si/RhSi(010) interface. It is shown that the Young's modulus and the workfunction of RhSi satisfy the generic sextic relation, proposed recently for elemental metals. The calculated p-SBH at the Si/RhSi interface is found to differ only by 0.04 eV in opposite limits, viz., no-pinning and strong pinning. We find that the p-SBH is reduced as much as by 0.28 eV due to vacancies at the interface. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4761994]

Manifestation of intermediate phase in mechanical properties: Nano-indentation studies on Ge-Te-Si bulk chalcogenide glasses

Nano-indentation studies have been undertaken on bulk Ge15Te85-xSix glasses (0 <= x <= 9), to estimate hardness, H and elastic modulus, E. It is found that E and H increase initially with the increase in the atomic percent of Si. Further, a plateau is seen in the composition dependence of E and H in the composition range 2 <= x <= 6. It is also seen that the addition of up to 2 at% Si increases the density rho of the glass considerably; however, further additions of Si lead to a near linear reduction in rho, in the range 2 <= x <= 6. Beyond x=6, rho increases again with Si content. The variation of molar volume V-m brings out a more fascinating picture. A plateau is seen in the intermediate phase suggesting that the molecular structure of the glasses is adapting to keep the count of constraints fixed in this particular phase. The observed variations in mechanical properties are associated with the Boolchand's intermediate phase in the present glassy system, in the composition range 2 <= x <= 6, suggested earlier from calorimetric and electrical switching studies. The present results reveal rather directly the existence of the intermediate phase in elastic and plastic properties of chalcogenide glasses. (C) 2012 Elsevier Ltd. All rights reserved.

Microstructure and mechanical properties of oxidation resistant suction cast Nb-Si-Al alloy

In this paper, we report a significant improvement in mechanical and oxidation properties of near eutectic Nb-Si alloys by the addition of aluminum (Al) and control of microstructural length scale. A comparative study of two alloys Nb-18.79at%Si and Nb-12.3at%Si-9at%Al were carried out. The processing for microstructure refinements were carried out by vacuum suction casting in water cooled thick copper mould. It is shown that addition of Al suppresses Nb3Si phase and promotes beta Nb5Si3 phase under nonequilibrium solidification condition. The microstructural length scale and in particular eutectic spacing reduces significantly to 50-100 nm in suction cast ternary alloy. A detailed TEM study shows the presence of delta-Nb11Si4 phase in Nb matrix. The hardness of Nb solid solution can be increased as a consequence to a level observed in Nb3Si intermetallic due to the well oriented precipitates. Compression test yields the ultimate strength of 1.8 +/- 0.1 GPa and engineering strain of 2.3 +/- 0.03%. In comparison, the binary Nb-18.79 at% Si alloy possesses an ultimate strength of 1.35 +/- 0.1 GPa and strain of 0.2 +/- 0.01% when processed under identical conditions. The latter exhibits coarser microstructural length scale (300-400 nm) and a brittle behavior. The indentation fracture toughness of Al containing suction cast alloy shows a value of 20.2 +/- 0.5 MPa root m which represents a major improvement over bulk Nb-Si eutectic alloy. The detailed thermal studies confirm a multifold improvement in oxidation resistance up to 1000 degrees C. (C) 2012 Elsevier B.V. All rights reserved.

Effect of Mg addition on microstructural, mechanical and environmental properties of Nb-Si eutectic composite

The paper reports the effect of addition of small amount of Mg on the mechanical and oxidation properties of Nb-Nb3Si eutectic composites in Nb-Si system under the condition of suction casting. Mg addition increases the volume fraction of primary dendrites of Nb solid solution. This phase contains significant amount of strengthening precipitates. Two different precipitates are identified. The large plate shaped precipitates are that of hcp phase, while fine coherent precipitates have the structure similar to recently identified delta-Nb11Si2 phase. The Mg addition improves both the strength and ductility of the composite at room temperature (similar to 1.4 GPa and similar to 5% engineering strain) as well as at 700 degrees C(similar to 1.2 GPa and similar to 7% engineering strain). The presence of Mg results in a complex barrier layer which significantly increases the oxidation resistance up to a temperature of at least 1000 degrees C. (C) 2012 Elsevier B.V. All rights reserved.