Influence of aging time of the starting solution on the physical properties of fluorine doped zinc oxide films deposited by a simplified spray pyrolysis technique

Fluorine doped zinc oxide (FZO) films were fabricated from fresh and aged (4, 8, 12 and 16 days) starting solutions using a simplified and low cost spray pyrolysis technique. The X-ray diffraction study showed that the preferential orientation is along the (0 0 2) plane for all the films irrespective of the age of the solution. The crystallite size calculated using the Scherrer’s formula is comparatively smaller only for the film prepared from the starting solution having aging time 4 days which may be due to the efficient incorporation of fluorine atoms into the ZnO lattice. This phenomenon is confirmed by the minimum resistivity value (3.14 × 10⁻² Ω cm) obtained in this particular case. The visible transmittance and the optical band gap values are found to be in the range of 63–83% and 3.20–3.31 eV, respectively. The optical transmittance is found to decrease gradually as the aging time of the solution increases and the optical band gap is found to be slightly higher in the case of the film prepared from the fourth day solution. The scanning electron microscopy results depicted that the microstructure of ZnO:F films are largely influenced by the aging of the starting solution.     

Stability of valence alternation pairs across the substoichiometric region at Ge/GeO2 interfaces

Through hybrid density functional calculations, we compare the Ge–Ge bond energy with the formation energy of a valence alternation pair as the O concentration varies across the Ge/GeO₂ interface. First, hole trapping energies are calculated for three atomistic models with different O concentrations: bulk Ge with isolated O atoms, amorphous GeO, and amorphous GeO₂ with an O vacancy. The reaction is then broken down in three steps involving the breaking of a Ge–Ge bond, charge transfer processes involving dangling bonds, and the formation of a threefold coordinated O atom. The energy of each elemental reaction is estimated through suitable model calculations. The charge transition levels resulting from this analysis agree with those obtained for the atomistic models. Our estimates indicate that hole trapping at low O concentrations occurs at no energy cost for p-type germanium owing to the formation of threefold-coordinated O atoms. Applied to n-type Ge, our analysis indicates that electron trapping in dangling bonds obtained from the breaking of Ge–Ge bonds is unfavorable. The formation energy of a valence alternation pair is evaluated and discussed in relation to previous results.     

Improved GaSb surfaces using a (NH4)2S/(NH4)2S04 solution

Bulk (1 0 0) n-GaSb surfaces have been treated with a sulphur based solution ((NH₄)₂S/(NH₄)₂SO₄) to which sulphur has been added, not previously reported for the passivation of GaSb surfaces. Au/n-GaSb Schottky barrier diodes (SBDs) fabricated on the treated material show significant improvement compared to that of the similar SBDs on the as-received material as evidenced by the lower ideality factor (n), higher barrier height (?_b) and lower contact resistance obtained. Additionally, the reverse leakage current, although not saturating, has been reduced by almost an order of magnitude at −0.2 V. The sample surfaces were studied by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The native oxide, Sb–O, present on the as-received material is effectively removed on treating with ([(NH₄)₂S/(NH₄)₂SO₄]+S) and (NH₄)₂S. Analysis of the as-received surface by XPS, prior to and after argon sputtering, suggests that the native oxide layer is ≤8.5 nm.     

Effect of thermal treatment in vacuum on Fe-doped SnO2 powders

A sample of 10 at% Fe-doped SnO₂ powder was prepared by mechanical alloying and then thermally treated at 773 K in vacuum. The fit of the diffraction patterns and X-ray absorption spectroscopy measurements revealed that the as milled sample was pure doped rutile. Fe dissolved into SnO₂ was found in Fe²⁺/Fe³⁺ ionic valence with mainly paramagnetic behavior. After the thermal treatment all techniques indicate the formation of the ternary Sn_0.36Fe_2.64O₄ spinel phase, which is responsible for the observed ferromagnetism.     

Structure of Na2O·MO·SiO2·CaF2 (M=Mg,Ca) oxyfluoride glasses

(9−x)CaO·xMgO·15Na₂O·60SiO₂·16CaF₂(x=0, 2, 4, 6, and 9) oxyfluoride glasses were prepared. Utilizing the Raman scattering technique together with ²⁹Si and ¹⁹F MAS NMR, the effect of alkaline metal oxides on the Q species of glass was characterized. Raman results show that as magnesia is added at the expense of calcium oxide, the disproportional reaction Q³→Q⁴+Q² (Qⁿ is a SiO₄ tetrahedron with n bridging oxygens) prompted due to the high ionic field strength of magnesia, magnesium oxide entered into the silicate network as tetrahedral MgO₄, and removed other modifying ions for charge compensation. This reaction was confirmed by ²⁹Si MAS NMR. ¹⁹F MAS NMR results show that fluorine exists in the form of mixed calcium sodium fluoride species in all glasses and no Si–F bonds were formed. As CaO is gradually replaced by MgO (x=6, 9), a proportion of the magnesium ions combines with fluorine to form the MgF⁺ species. Meanwhile, some part of Na⁺ ions complex F⁻ in the form of F–Na(6).     

Raman scattering of MnOx?CeOx composite catalysts: structural aspects and laser‐heating effects

Composite MnO_x CeO_x catalysts (Mn_at: Ce_at = 1) synthesized via the redox and coprecipitation routes were comparatively characterized by micro‐Raman spectroscopy using a laser irradiation power ranging between 0.6 and 4.2 mW. A quasi‐molecular dispersion of the oxide species determines a major and irreversible structural rearrangement of the redox MnO_x CeO_x system because of severe heating effects for laser power in excess of 0.6 mW. The X‐ray diffraction data of samples calcined in the range of 673 1273 K confirm that the micro‐Raman characterization of the composite MnO_x CeO_x systems requires an adequate minimization of the irradiation power to prevent the strong sintering and restructuring phenomena due to laser‐heating effects. Copyright © 2011 John Wiley & Sons, Ltd.     

Mechanisms and origin of multiferroicity

Motivated by the potential applications of their intrinsic cross-coupling properties, the interest in multiferroic materials has constantly increased recently, leading to significant experimental and theoretical advances. From the theoretical point of view, recent progresses have allowed one to identify different mechanisms responsible for the appearance of ferroelectric polarization coexisting—and coupled—with magnetic properties. This chapter aims at reviewing the fundamental mechanisms devised so far, mainly in transition-metal oxides, which lie at the origin of multiferroicity.     

Methods for calculating the desorption rate of an isolated molecule from a surface: Water on MgO(0 0 1)

We present two types of Molecular Dynamics (MD) simulation for calculating the desorption rate of molecules from a surface. In the first, the molecules move freely between two surfaces, and the desorption rate is obtained either by counting the number of desorption events in a given time, or by looking at the average density of the molecules as a function of distance from the surface and then applying transition state theory (TST). In the second, the potential of mean force (PMF) for a molecule is determined as a function of distance from the surface and the desorption rate is obtained by means of TST. The methods are applied to water on the MgO(0 0 1) surface at low coverage. Classical potentials are used so that long simulations can be performed, to minimise statistical errors. The two sets of MD simulations agree well at high temperatures. The PMF method reproduces the 0 K adsorption energy of the molecule to within 5 meV, and finds that the well depth of the PMF is not linear with temperature. This implies the prefactor frequency f in the Polanyi-Wigner equation is a function of temperature, increasing at lower temperatures due to the reduction of the available configuration space associated with an adsorbed molecule compared with a free molecule.     

Low-field magnetoresistance of Ag-substituted perovskite-type manganites

A series of bulk polycrystalline Nd_1−xAg_xMnO₃ samples were prepared by conventional solid-state reaction processing, for x between 0.1 and 0.5. The structure, magnetism, and magnetoresistance (MR) of the samples are investigated. The X-ray diffraction patterns show that the x=0.1 sample is a single perovskite structure, while x0.167, samples consist of a ferromagnetic perovskite phase and two nonmagnetic phases, Ag and Mn₃O₄. The MR of Nd_1−xAg_xMnO₃ is enhanced by increasing the composition of Ag. Compared with the sample of x=0.1, the x=0.5 sample has a significantly larger value of low-field MR. The enhanced low-field MR is related to the spin-dependent scattering of spin-polarized electrons at the interfaces between the perovskite grains and silver granules.