Electron mobility in few-layer MoxW1-xS2

Heterostructures of two-dimensional (2D) layered materials are increasingly being explored for electronics in order to potentially extend conventional transistor scaling and to exploit new device designs and architectures. Alloys form a key underpinning of any heterostructure device technology and therefore an understanding of their electronic properties is essential. In this paper, we study the intrinsic electron mobility in few-layer MoxW1-xS2 as limited by various scattering mechanisms. The room temperature, energy-dependent scattering times corresponding to polar longitudinal optical (LO) phonon, alloy and background impurity scattering mechanisms are estimated based on the Born approximation to Fermi's golden rule. The contribution of individual scattering rates is analyzed as a function of 2D electron density as well as of alloy composition in MoxW1-xS2. While impurity scattering limits the mobility for low carrier densities (<2-4x10(12) cm(-2)), LO polar phonon scattering is the dominant mechanism for high electron densities. Alloy scattering is found to play a non-negligible role for 0.5 < x < 0.7 in MoxW1-xS2. The LO phonon-limited and impurity-limited mobilities show opposing trends with respect to alloy mole fractions. The understanding of electron mobility in MoxW1-xS2 presented here is expected to enable the design and realization of heterostructures and devices based on alloys of MoS2 andWS(2).

Properties of the correlated electronic states of pyrene and hydrogenated pyrene

Approximate calculations are reported on pyrene within the PPP model Hamiltonian using a novel restricted CI scheme which employs both molecular orbital and valence bond techniques. Also reported are detailed full CI results of the PPP model on 2,7-dihydropyrene obtained using the valence bond method. Spectral studies, charge and spin density calculations in ground and excited states, and ring current calculations in the ground state of the molecules are presented. In pyrene, the calculated excitation energies are in good agreement with experiment. The closed structure pi-conjugated molecule pyrene appears to show smaller distortions from the ground state geometry compared with the open structure pi-conjugated molecule 2,7-dihydropyrene. The ground state equilibrium structure of 2,7-dihydropyrene can be viewed as two hexatriene molecules connected by a vinyl crosslink, as is evident from bond order and ring current calculations. This is consistent with the only Kekule resonant structure possible for this molecule.

Octabromotetraphenylporphyrin and its metal derivatives: Electronic structure and electrochemical properties

The free-base octabromotetraphenylporphyrin (H2OBP) has been prepared by a novel bromination reaction of (meso-tetraphenylporphyrinato)copper(II). The metal [V(IV)O, Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Ag(II), Pt(II)] derivatives exhibit interesting electronic spectral features and electrochemical redox properties. The electron-withdrawing bromine substituents at the pyrrole carbons in H2OBP and M(OBP) derivatives produce remarkable red shifts in the Soret (50 nm) and visible bands (100 nm) of the porphyrin. The low magnitude of protonation constants (pK3 = 2.6 and pK4 = 1.75) and the large red-shifted Soret and visible absorption bands make the octabromoporphyrin unique. The effect of electronegative bromine substituents at the peripheral positions of the porphyrin has been quantitatively analyzed by using the four-orbital approach of Gouterman. A comparison of MO parameters of MOBP derivatives with those of the meso-substituted tetraphenylporphyrin (M(TPP)) and unsubstituted porphine (M(P)) derivatives provides an explanation for the unusual spectral features. The configuration interaction matrix element of the M(OBP) derivatives is found to be the lowest among the known substituted porphyrins, indicating delocalization of ring charge caused by the increase in conjugation of p orbitals of the bromine onto the ring orbitals. The electron-transfer reactivities of the porphyrins have been dramatically altered by the peripheral bromine substituents, producing large anodic shifts in the ring and metal-centered redox potentials. The increase in anodic shift in the reduction potential of M(OBP)s relative to M(TPP)s is found to be large (550 mV) compared to the shift in the oxidation potential (300 mV). These shifts are interpreted in terms of the resonance and inductive interactions of the bromine substituents.

Effect of the Edge Type and Strain on the Structural, Electronic and Magnetic Properties of the BNRs

We present the effect of edge structures on the edge energy and stress of BN nanoribbons. Ab initio density functional calculations show that the armchair edge is lower in energy than the zigzag edge by 0.43 eV/angstrom. Both types of the edges are under the compressive stress. The zigzag edges are mechanically more stable than the armchair edges. Based on the calculated edge energies, the equilibrium shape of the BN flakes are found to be regular hexagonal, and dominated by the armchair edges. The zigzag ribbons are found to be half-metallic, whereas the armchair ribbons are semiconducting.

Shape Effect on Electronic and Photovoltaic Properties of CdS Nanocrystals

Changes in electronic and photovoltaic properties of semiconductor nanocrystals predominantly due to changes in shape are discussed here. Cadmium sulfide (CdS) semiconductor nanocrystals of various shapes (tetrapod, tetrahedron, sphere and rod) obtained using an optimized solvothermal process exhibited a mixed cubic (zinc blende) and hexagonal (wurtzite) crystal structure. The simultaneous presence of the two crystal phases in varying amounts is observed to play a pivotal role in determining both the electronic and photovoltaic properties of the CdS nanocrystals. Light to electrical energy conversion efficiencies (measured in two-electrode configuration laboratory solar cells) remarkably decreased by one order in magnitude from tetrapod -> tetrahedron -> sphere -> rod. The tetrapod-CdS nanocrystals, which displayed the highest light to electrical energy conversion efficiency, showed a favorable shift in position of the conduction band edge leading to highest rate of electron injection (from CdS nanocrystal to the wide band gap semiconductor viz, titanium dioxide, TiO2) and lowest rate of electron-hole recombination (higher free electron lifetimes).

Effect of strain on electronic and thermoelectric properties of few layers to bulk MoS2

The sensitive dependence of the electronic and thermoelectric properties of MoS2 on applied strain opens up a variety of applications in the emerging area of straintronics. Using first-principles-based density functional theory calculations, we show that the band gap of a few layers of MoS2 can be tuned by applying normal compressive (NC) strain, biaxial compressive (BC) strain, and biaxial tensile (BT) strain. A reversible semiconductor-to-metal transition (S-M transition) is observed under all three types of strain. In the case of NC strain, the threshold strain at which the S-M transition occurs increases when the number of layers increase and becomes maximum for the bulk. On the other hand, the threshold strain for the S-M transition in both BC and BT strains decreases when the number of layers increase. The difference in the mechanisms for the S-M transition is explained for different types of applied strain. Furthermore, the effect of both strain type and the number of layers on the transport properties are also studied using Botzmann transport theory. We optimize the transport properties as a function of the number of layers and the applied strain. 3L- and 2L-MoS2 emerge as the most efficient thermoelectric materials under NC and BT strain, respectively. The calculated thermopower is large and comparable to some of the best thermoelectric materials. A comparison among the feasibility of these three types of strain is also discussed.

Electronic and Magnetic Properties of Yttrium-doped Silicon Carbide Nanotubes: Density Functional Theory Investigations

The electronic structure of yttrium-doped Silicon Carbide Nanotubes has been theoretically investigated using first principles density functional theory (DFT). Yttrium atom is bonded strongly on the surface of the nanotube with a binding energy of 2.37 eV and prefers to stay on the hollow site at a distance of around 2.25 angstrom from the tube. The semi-conducting nanotube with chirality (4, 4) becomes half mettalic with a magnetic moment of 1.0 mu(B) due to influence of Y atom on the surface. There is strong hybridization between d orbital of Y with p orbital of Si and C causing a charge transfer from d orbital of the Y atom to the tube. The Fermi level is shifted towards higher energy with finite Density of States for only upspin channel making the system half metallic and magnetic which may have application in spintronic devices.

Tailoring of Electronic Structure and Thermoelectric Properties of a Topological Crystalline Insulator by Chemical Doping

Topological crystalline insulators (TCIs) are a new quantum state of matter in which linearly dispersed metallic surface states are protected by crystal mirror symmetry. Owing to its vanishingly small bulk band gap, a TCI like Pb0.6Sn0.4Te has poor thermoelectric properties. Breaking of crystal symmetry can widen the band gap of TCI. While breaking of mirror symmetry in a TCI has been mostly explored by various physical perturbation techniques, chemical doping, which may also alter the electronic structure of TCI by perturbing the local mirror symmetry, has not yet been explored. Herein, we demonstrate that Na doping in Pb0.6Sn0.4Te locally breaks the crystal symmetry and opens up a bulk electronic band gap, which is confirmed by direct electronic absorption spectroscopy and electronic structure calculations. Na doping in Pb0.6Sn0.4Te increases p-type carrier concentration and suppresses the bipolar conduction (by widening the band gap), which collectively gives rise to a promising zT of 1 at 856 K for Pb0.58Sn0.40Na0.02Te. Breaking of crystal symmetry by chemical doping widens the bulk band gap in TCI, which uncovers a route to improve TCI for thermoelectric applications.

Lifshitz transition and modulation of electronic and transport properties of bilayer graphene by sliding and applied normal compressive strain

Using density functional theory (DFT) we investigate the changes in electronic and transport properties of graphene bilayer caused by sliding one of the layers. Change in stacking pattern breaks the lattice symmetry, which results in Lifshitz transition together with the modulation of the electronic structure. Going from AA to AB stacking by sliding along armchair direction leads to a drastic transition in electronic structure from linear to parabolic dispersion. Our transport calculations show a significant change in the overall transmission value for large sliding distances along zigzag direction. The increase in interlayer coupling with normal compressive strain increases the overlapping of conduction and valence band, which leads to further shift in the Dirac points and an enhancement in the Lifshitz transition. The ability to tune the topology of band structure by sliding and/or applying normal compressive strain will open doors for controlled tuning of many physical phenomenon such as Landau levels and quantum Hall effect in graphene. (C) 2015 Elsevier Ltd. All rights reserved.

Giant Magnetoresistance and Related Properties of Rare Earth Manganates and Other Oxide Systems

Giant magnetoresistance (GMR), which was until recently confined to magnetic layered and granular materials, as well as doped magnetic semiconductors, occurs in manganate perovskites of the general formula Ln(1-x)A(x)MnO(3) (Ln = rare earth; A = divalent ion). These manganates are ferromagnetic at or above a certain value of x (or Mn4+ content) and become metallic at temperatures below the curie temperature, T-c. GMR is generally a maximum close to T-c or the insulator-metal (I-M) transition temperature, T-im. The T-c and %MR are markedly affected by the size of the A site cation, [r(A)], thereby affording a useful electronic phase diagram when T-c or T-im is plotted against [r(A)]. We discuss GMR and related properties of manganates in polycrystalline, thin-film, and single-crystal forms and point out certain commonalities and correlations. We also examine some unusual features in the electron-transport properties of manganates, in particular charge-ordering effects. Charge ordering is crucially dependent on [r(A)] or the e(g) band width, and the charge-ordered insulating state transforms to a metallic ferromagnetic state on the application of a magnetic field.

Donor properties of metallomacrocyclic tetrapyrrole pigments with sym-trinitrobenzene

The interactions of metallo derivatives of macrocyclic tetrapyrrole pigments, pheophytin a (pheo), phthalocyanin (phth), and tetraphenylporphyrin (TPP) with sym-trinitrobenzene (TNB) have been studied with use of spectroscopic methods. These macrocyles form 1:l molecular complexw with the acceptor. The association constants (K) for the interactions follow the decreasing order of binding as pheo > phth > TPP. The divalent metal ions influence the values of K for the various metallo TPP derivatives, and the relative order of stabilities decrease as Co > Cu = VO > Ni > Zn. The stereochemistry of M(TPP) and the electronic configuration of the metal ions are shown to contribute to the magnitudes of K. The acceptor strongly quenches the fluorescence of the metallo macrocycles, and the quenching constant decreases as pheo > phth > TPP. The formation of exciplexes is postulated on the basis of the rate of bimolecular quenching constants and solvent effects.

Synthesis and physico-chemical properties of diruthenium(III, II) tetra-aryl carboxylato compounds

Monochloro-tetra-μ-aryl-carboxylatodiruthenium(III, II) compounds Ru2Cl (O2CAr)4 (Ar = -C6H5; -C6H4-p-OCH3), are prepared and characterized. The compounds have magnetic moments that correspond to three unpaired spins per dimer. The Rusingle bondRu bond order is 2.5 and the ground electronic configuration is σ2π4δ2(δ*π*)3. The visible spectral band is observed at ca 450 nm along with a shoulder near 580 nm in DMF solution. The compounds undergo a one-electron Ru(III)Ru(II) → Ru(II)Ru(II) quasi-reversible reduction in DMF near 0.0 V vs sce.

Estimation Of Properties Of Rare-Gas Solids From Compression Characteristics Of Closed-Shell Ions

We present a unified approach to repulsion in ionic and van der Waals solids based on a compressible-ion/atom model. Earlier studies have shown that repulsion in ionic crystals can be viewed as arising from the compression energy of ions, described by two parameters per ion. Here we obtain the compression parameters of the rare-gas atoms Ne. Ar. Kr and Xe by interpolation using the known parameters of related equi-electronic ions (e.g. Ar from S2-. Cl-, K- and Ca2-). These parameters fit the experimental zero-temperature interatomic distances and compressibilities of the rare-gas crystals satisfactorily. A hightemperature equation of state based on an Einstein model of thermal motions is used to calculate the thermal expansivities, compressibilities and their temperature derivatives for Ar. Kr and Xe. It is argued that an instability at higher temperatures represents the limit to which the solid can be superheated. beyond which sublimation must occur.

Influence of Band Non-Parabolicity on Few Ballistic Properties of III-V Quantum Wire Field Effect Transistors Under Strong Inversion

A simplified yet analytical approach on few ballistic properties of III-V quantum wire transistor has been presented by considering the band non-parabolicity of the electrons in accordance with Kane's energy band model using the Bohr-Sommerfeld's technique. The confinement of the electrons in the vertical and lateral directions are modeled by an infinite triangular and square well potentials respectively, giving rise to a two dimensional electron confinement. It has been shown that the quantum gate capacitance, the drain currents and the channel conductance in such systems are oscillatory functions of the applied gate and drain voltages at the strong inversion regime. The formation of subbands due to the electrical and structural quantization leads to the discreetness in the characteristics of such 1D ballistic transistors. A comparison has also been sought out between the self-consistent solution of the Poisson's-Schrodinger's equations using numerical techniques and analytical results using Bohr-Sommerfeld's method. The results as derived in this paper for all the energy band models gets simplified to the well known results under certain limiting conditions which forms the mathematical compatibility of our generalized theoretical formalism.

Metal complexes of thiophene 2-thiocarboxamide. Proton and 13C NMR, IR and electronic spectral studies

The complexes of thiophene 2-thiocarboxamide (TTCA) with some metal chlorides and bromides [M = Ni(II), Zn(II), Cd(II), Hg(II) and Cu(I)] are described. Elemental analyses, magnetic susceptibilities and conductance studies, electronic, IR, proton and 13C magnetic resonance spectra are reported. The results suggest exclusive coordination of TTCA through the thiocarbonyl sulfur. The influence of the thiophene ring on the donor properties of the thioamide are discussed.