Exploring the Colour of 3d Transition-Metal Ions in Trigonal Bipyramidal Coordination: Identification of Purple-Blue (CoO5) and Beige-Red (NiO5) Chromophores in LiMgBO3 Host

In an attempt to develop new coloured inorganic oxides, we have investigated the substitution of 3d transition-metal ions in LiMgBO3 host where Mg-II has a trigonal bipyramidal (TBP) oxygen coordination]. We find that single-phase materials are formed for (LiMg1-xCoxBO3)-B-II (0 < x 1.0), (LiMg1-xNixBO3)-B-II (0 < x 0.1), (LiMg1-xCuxBO3)-B-II (0 < x 0.1) and also (Li1-xMg1-xFexBO3)-B-III (0 < x 0.1) of which the Co-II and Ni-II derivatives are strongly coloured, purple-blue and beige-red, respectively, thus identifying TBP CoO5 and NiO5 as new chromophores for these colours.

Measuring the magnetic-field-dependent chemical potential of a low-density three-dimensional electron gas in n-GaAs and extracting its magnetic susceptibility

We report the magnetic-field-dependent shift of the electron chemical potential in bulk, n-type GaAs at room temperature. A transient voltage of similar to 100 mu V was measured across a Au-Al2O3-GaAs metal-oxide-semiconductor capacitor in a pulsed magnetic field of similar to 6 T. Several spurious voltages larger than the signal that had plagued earlier researchers performing similar experiments were carefully eliminated. The itinerant magnetic susceptibility of GaAs is extracted from the experimentally measured data for four different doping densities, including one as low as 5 x 10(15) cm(-3). Though the susceptibility in GaAs is dominated by Landau-Peierls diamagnetism, the experimental technique demonstrated can be a powerful tool for extracting the total free carrier magnetization of any electron system. The method is also virtually independent of the carrier concentration and is expected to work better in the nondegenerate limit. Such experiments had been successfully performed in two-dimensional electron gases at cryogenic temperatures. However, an unambiguous report on having observed this effect in any three-dimensional electron gas has been lacking. We highlight the 50 year old literature of various trials and discuss the key details of our experiment that were essential for its success. The technique can be used to unambiguously yield only the itinerant part of the magnetic susceptibility of complex materials such as magnetic semiconductors and hexaborides, and thus shed light on the origin of ferromagnetism in such systems.

Transition metal-free Minisci reaction promoted by NCS, and TBHP: acylation of heteroarenes

A method for acylation for heteroarenes under metal-free conditions has been described using NCS as an additive and TBHP as an oxidant. This method has been successfully employed in acylation of a variety of aldehyde with heteroarenes. The application of the method has been illustrated in synthesizing isoquinoline derived natural products. This strategy provides an efficient, mild and inexpensive method for acylation of heteroarenes. (C) 2015 Elsevier Ltd. All rights reserved.

High temperature thermoelectric properties of Zr and Hf based transition metal dichalcogenides: A first principles study

We investigate the electronic and thermal transport properties of bulk MX2 compounds (M = Zr, Hf and X = S, Se) by first-principles calculations and semi-classical Boltzmann transport theory. The band structure shows the confinement of heavy and light bands along the out of plane and in-plane directions, respectively. This results in high electrical conductivity (sigma) and large thermopower leading to a high power factor (S-2 sigma) for moderate n-type doping. The phonon dispersion demonstrates low frequency flat acoustical modes, which results in low group velocities (v(g)). Consequently, lowering the lattice thermal conductivity (kappa(latt)) below 2 W/m K. Low kappa(latt) combined with high power factor results in ZT > 0.8 for all the bulk MX2 compounds at high temperature of 1200 K. In particular, the ZT(max) of HfSe2 exceeds 1 at 1400 K. Our results show that Hf/Zr based dichalcogenides are very promising for high temperature thermoelectric application. (C) 2015 AIP Publishing LLC.

Percolative switching in transition metal dichalcogenide field-effect transistors at room temperature

We have addressed the microscopic transport mechanism at the switching or `on-off' transition in transition metal dichalcogenide (TMDC) field-effect transistors (FETs), which has been a controversial topic in TMDC electronics, especially at room temperature. With simultaneous measurement of channel conductivity and its slow time-dependent fluctuation (or noise) in ultrathin WSe2 and MoS2 FETs on insulating SiO2 substrates where noise arises from McWhorter-type carrier number fluctuations, we establish that the switching in conventional backgated TMDC FETs is a classical percolation transition in a medium of inhomogeneous carrier density distribution. From the experimentally observed exponents in the scaling of noise magnitude with conductivity, we observe unambiguous signatures of percolation in a random resistor network, particularly, in WSe2 FETs close to switching, which crosses over to continuum percolation at a higher doping level. We demonstrate a powerful experimental probe to the microscopic nature of near-threshold electrical transport in TMDC FETs, irrespective of the material detail, device geometry, or carrier mobility, which can be extended to other classes of 2D material-based devices as well.

Reagent-switch controlled metal-free intermolecular geminal diamination and aminooxygenation of vinylarenes

We report here the first general method for the geminal diamination and an intermolecular metal-free, geminal aminooxygenation of vinylarenes using hypervalent iodine reagent. A new m-CPBA mediated geminal aminooxygenation is also reported. A novel reagent-switch for the control of migrating group by controlling the two independent geminal addition paths is developed. Deuterium labelling studies and the control studies have provided unambiguous evidences for the phenyl migration and hydride migration in the oxidative geminal difunctionalization process mediated by Phl(OCOCF3)(2) and m-CPBA, respectively through a semi-pinacol rearrangement. (C) 2016 Elsevier Ltd. All rights reserved.

NH3 adsorption on PtM (Fe, Co, Ni) surfaces: Cooperating effects of charge transfer, magnetic ordering and lattice strain

Adsorption of a molecule or group with an atom which is less electronegative than oxygen (0) and directly interacting with the surface is very relevant to development of PtM (M = 3d-transition metal) catalysts with high activity. Here, we present theoretical analysis of the adsorption of NH3 molecule (N being less electronegative than 0) on (111) surfaces of PtM (Fe, Co, Ni) alloys using the first principles density functional approach. We find that, while NH3-Pt interaction is stronger than that of NH3 with the elemental M-surfaces, it is weaker than the strength of interaction of NH3 with M-site on the surface of PtM alloy. (C) 2016 Published by Elsevier B.V.

Design Optimization of Thin-Film Transistors Based on a Metal-Substrate-Semiconductor Architecture for High DC Voltage Sensing

We discuss the potential application of high dc voltage sensing using thin-film transistors (TFTs) on flexible substrates. High voltage sensing has potential applications for power transmission instrumentation. For this, we consider a gate metal-substrate-semiconductor architecture for TFTs. In this architecture, the flexible substrate not only provides mechanical support but also plays the role of the gate dielectric of the TFT. Hence, the thickness of the substrate needs to be optimized for maximizing transconductance, minimizing mechanical stress, and minimizing gate leakage currents. We discuss this optimization, and develop n-type and p-type organic TFTs using polyvinyldene fluoride as the substrate-gate insulator. Circuits are also realized to achieve level shifting, amplification, and high drain voltage operation.

Density functional theory based study of chlorine doped WS2-metal interface

Investigation of a transition metal dichalcogenide (TMD)-metal interface is essential for the effective functioning of monolayer TMD based field effect transistors. In this work, we employ the Density Functional Theory calculations to analyze the modulation of the electronic structure of monolayer WS2 with chlorine doping and the relative changes in the contact properties when interfaced with gold and palladium. We initially examine the atomic and electronic structures of pure and doped monolayer WS2 supercell and explore the formation of midgap states with band splitting near the conduction band edge. Further, we analyze the contact nature of the pure supercell with Au and Pd. We find that while Au is physiosorbed and forms n-type contact, Pd is chemisorped and forms p-type contact with a higher valence electron density. Next, we study the interface formed between the Cl-doped supercell and metals and observe a reduction in the Schottky barrier height (SBH) in comparison to the pure supercell. This reduction found is higher for Pd in comparison to Au, which is further validated by examining the charge transfer occurring at the interface. Our study confirms that Cl doping is an efficient mechanism to reduce the n-SBH for both Au and Pd, which form different types of contact with WS2. (C) 2016 AIP Publishing LLC.

Enhancing photoresponsivity using MoTe2-graphene vertical heterostructures

MoTe2 with a narrow band-gap of similar to 1.1 eV is a promising candidate for optoelectronic applications, especially for the near-infrared photo detection. However, the photo responsivity of few layers MoTe2 is very small (<1mAW(-1)). In this work, we show that a few layer MoTe2-graphene vertical heterostructures have a much larger photo responsivity of similar to 20mAW(-1). The trans-conductance measurements with back gate voltage show on-off ratio of the vertical transistor to be similar to(0.5-1) x 10(5). The rectification nature of the source-drain current with the back gate voltage reveals the presence of a stronger Schottky barrier at the MoTe2-metal contact as compared to the MoTe2-graphene interface. In order to quantify the barrier height, it is essential to measure the work function of a few layers MoTe2, not known so far. We demonstrate a method to determine the work function by measuring the photo-response of the vertical transistor as a function of the Schottky barrier height at the MoTe2-graphene interface tuned by electrolytic top gating. (C) 2016 AIP Publishing LLC.

A noble and single source precursor for the synthesis of metal-rich sulphides embedded in an N-doped carbon framework for highly active OER electrocatalysts

Here, we demonstrate a green and environment-friendly pyrolysis route for the synthesis of metal-rich sulphide embedded in an N-doped carbon (NC) framework in the absence of sulphide ions (S2-). The metal-chelate complex (tris(ethylenediamine) metal(II) sulfate) serves as a new and single source precursor for the synthesis of earth abundant and non-precious hybrid structures such as metal-rich sulphides Co9S8@NC and Ni3S2@ NC when M-II = Co2+ and Ni2+ and counter sulphate (SO42-) ions are the source of S. Both the hybrids show superior OER activity as compared to commercial RuO2.