Synthesis of dimension-tunable ZnO nanostructures via the design of zinc hydroxide precursors

A facile synthesis route is presented to achieve dimension-tunable ZnO nanostructures by the design of zinc hydroxide precursors under the surfactant-free condition. From three types of zinc hydroxide precursors, namely, crystalline Zn(OH)(NO₃)(H₂O) nanobelts, amorphous zinc hydroxides microparticles and soluble Zn(OH)^2-₄\mathrm{Zn}(\mathrm{OH})^{2-}_{4} species, the porous ZnO nanosheets, ZnO nanoparticles and ZnO nanowires can be achieved, respectively. The porous ZnO nanosheets exhibit large polar surface area. Thermal analysis indicates that the crystalline Zn(OH)(NO₃)(H₂O) nanobelts were converted to the porous ZnO nanosheets by in situ lattice reconstruction, which was attributed to the unique fibrous structure of Zn(OH)(NO₃)(H₂O) nanobelts. The as-prepared dimension-tunable ZnO nanostructures have potential applications in solar cells, photocatalysis, novel chemical and biological sensors, etc.     

Field emission studies of oxygen on silver tips

Clean [111] oriented silver field emitting tips have been exposed to oxygen at 10^?3 Torr for 1 min at temperatures ranging from ? 170 to 200°C. From 50 to 200°C, an adsorption structure is formed that is stable in oxygen. The structure is characterized by intensely emitting regions on either side of enlarged {110}, {210} and {310} faces and a dark region in the (111)-{100} zone line directions. For adsorption from ? 170 to 200°C, the structure of the patterns depends distinctly on the adsorption temperature because the coverages are different and adsorption is activated. Oxygen adsorption at 10^?3 Torr for 1 min at 0°C causes an increase in the average work function of 1.15 eV. At 0°C, silver was exposed increasingly at 10^?6 Torr until 6100 L was reached. The work function increased progressively by 0.61 eV for this exposure. The {111}, {100}, {311}, {211} and {533} faces are attacked first. Then, the {110} faces are attacked followed by the {210} {310} and {320}. Heating of the adsorption layer formed at 0°C produced no changes in pattern and work function up to 100°C. Between 100 and 200°C, a strong decrease in work function and changes in the pattern result from oxygen penetration into the bulk.     

A combined ab initio and atomistic simulation study of the surface and interfacial structures and energies of hydrated scheelite: introducing a CaWO4 potential model

Density functional theory (DFT) calculations of the calcium tungstate material scheelite CaWO₄ have shown that water introduced into the bulk material remains undissociated and leads to swelling and layering of the structure, a behaviour which may resemble silicate clays more than three-dimensional poly-anionic materials, but which results in a structure that is even more similar to a rare hydrous calcium carbonate phase--a finding which suggests the existence of semi-crystalline hydrous pre-cursor phases to the dehydrated scheelite material. An interatomic potential model was derived for CaWO₄ which adequately reproduces structural and physical properties of the material and is in good agreement with the DFT calculations in respect of the structure and energy of hydration (DFT: 85 kJ mol⁻¹, atomistic: 105 kJ mol⁻¹). Atomistic simulations of a range of scheelite surfaces confirm the dominance of the experimental {1 0 1} and {0 0 1} cleavage planes in the morphology of the dry crystal and the presence of the experimentally found {1 0 3} and {1 0 1} surfaces in the hydrated morphology. Hydration of the surfaces shows non-Langmuir behaviour, where the interactions between surface calciums and oxygen atoms of the water molecules outweigh hydrogen-bonding to the surface oxygen atoms or intermolecularly within the water layer. The hydration energies indicate physisorption of water, ranging from 22 kJ mol⁻¹ on the {0 0 1} surface to 78 kJ mol⁻¹ on the more reactive {1 0 3} surface.     

Preparation and characterization of nanocrystalline ZnO particles from a hydrothermal process

Rod-like ZnO nanoparticles were prepared by the hydrolysis of zinc acetate under heating in diethylene glycol (DEG). Structural characterization of the synthesized powders was investigated by XRD, FT-IR, electron paramagnetic resonance (EPR) and transmission electron microscopy (TEM). The size of the particles increased as the amount of H₂O added increased in the nano size range. The average crystallite size calculated from the XRD patterns varied from 6 to 64 nm corresponding to the amount of H₂O added. The ZnO nanopartilces possess the wurtzite type crystallographic structure. It was found that these ZnO nanoparticles had singly ionized oxygen vacancy defect () and superoxide ions from the EPR investigations. A strong near UV emission of the ZnO nanoparticles at about 380 nm was observed and its intensity decreased as the amount of H₂O increased. This emission of ZnO nanoparticles is found to be particles size dependent due to the confinement effect. A green emission at about 540 nm due to the recombination of electrons trapped at singly ionized oxygen vacancies defect () appeared when the amount of H₂O increased. The intensity of the green emission increases as the concentration of increases.     

Adsorption of oxygen on a Cu{110} surface with and without the influence of A keV Ne+ beam: Stage I: Coverages up to half a monolayer

Low Energy Ion Scattering has been used to study the interaction of molecular oxygen with a Cu{110} surface. The amount of adsorbed atomic oxygen was monitored by the 4 keV Ne⁺¦O reflection signal. In the first adsorption stage (coverage less than half a monolayer) the sticking probability varied proportional to the number of empty adsorption sites: S = S₀ (1 ? $\text{}\text{?}$gq). It turned out not to be influenced by the Ne⁺ bombardment. The initial sticking probability S₀ was found to be ≈ 0.24. In this first adsorption stage the oxygen-covered surface is reconstructed according to the “missing row” model, leading to a (2 × 1) LEED pattern.     

Theoretical study on adsorption of Au and hydrated Au cations on clean Si(1 1 1) surface

To model the adsorption of Au⁺ cation in aqueous solution on the semiconductor surface, the interactions of Au⁺ and hydrated Au⁺ cations with clean Si(1 1 1) surface were investigated by using hybrid density functional theory (B3LYP) and Møller-Plesset second-order perturbation (MP2) methods. Si(1 1 1) surface was described with Si₇H₁₁, Si₁₁H₁₇ and Si₂₂H₂₁ clusters. The effect of the basis set superposition error (BSSE) was taken into account by applying the counterpoise correction. The calculated results indicated that the binding energies between hydrated Au⁺ cations and clean Si(1 1 1) surface are large, suggesting a strong interaction between hydrated Au⁺ cations and the semiconductor surface. The bonding nature of the chemical adsorption of Au⁺ to Si surface can be classified as partial covalent as well as ionic bonding. As the number of water molecules increases, the water molecules form hydrogen bond network with one another and only one water molecule binds directly to the Au⁺ cation. The Au⁺ cation in aqueous solution will safely attach to the clean Si(1 1 1) surface.     

Ultrafast delocalization of hydrogen atoms in allene in intense laser fields

Ultrafast delocalization of hydrogen atoms in allene (CH₂=C=CH₂) induced by intense laser fields was investigated by the Coulomb explosion coincidence momentum imaging method. On the basis of the kinetic energy distributions of the fragment ions produced through the two three-body Coulomb explosion pathways, C₃H₄³⁺ ? H⁺ + CH⁺ + C₂H₂⁺\mathrm{C}_{3}\mathrm{H}_{4}^{3+} \rightarrow \mathrm{H}^{+} + \mathrm{CH}^{+} + \mathrm{C}_{2}\mathrm{H}_{2}^{+} and C₃H₄³⁺ ? H⁺ + C₂H⁺ +CH₂⁺\mathrm{C}_{3}\mathrm{H}_{4}^{3+} \rightarrow \mathrm{H}^{+} + \mathrm{C}_{2}\mathrm{H}^{+} +\mathrm{CH}_{2}^{+}, and the proton maps for both pathways, it was shown that the decomposition proceeds in a stepwise manner as well as in a concerted manner. The time scale of the hydrogen migration within an allene molecule was estimated to be ∼20 fs.     

Evaluating the electric property of different crystal faces and enhancing the Raman scattering of Cu2O microcrystal by depositing Ag on the surface

The surface electric property of Cu₂O microcrystal affects the interaction of facets with substance in the aqueous solution, and hence plays a key role in determining the photocatalytic activity. In this paper, the capability of Cu₂O microcrystals with exclusive {111}, {110} or both lattice surfaces in reducing Ag⁺ to Ag⁰ were investigated. Ag particles selectively deposited on {111} surfaces of Cu₂O, while not on {110} surfaces. The different behaviors of the two surfaces are mainly attributed to their different electric properties: negatively-charged {111} surfaces absorb Ag⁺ ions while positively-charged {110} surfaces repel them. Raman scattering of Cu₂O {111} surfaces was enhanced by the photo-deposition of Ag particles.     

Twin Boundaries in Zinc Oxide with Additions of Gallium Oxide

Twin boundaries (TBs) in ZnO sintered with small additions of Ga₂O₃ have been characterized with advanced methods of transmission electron microscopy (TEM). The TBs and accompanying inversion domain boundaries are on {011¯3} planes of ZnO. The Ga content of the TB corresponds to an effectively half occupied {011¯3} plane determined from compositional maps calculated from electron spectroscopic images using electron filtering TEM. The structure of the TBs were investigated by high-resolution TEM, and images of focus series were used to reconstruct the complex electron wave. Simulated electron waves based on structure models of the TB were quantitatively compared with the reconstructed wave to identify and to refine atom positions. The twins can be considered to be created by a mirror operation on a {011¯3} plane of ZnO, and two alternating closed-packed polyhedral clusters of oxygen ions can be identified as building units of the TB structure. Unit 1 is occupied with Zn²⁺ by simply continuing ZnO₄ tetrahedra of the same type from both crystals to the TB. Using arguments of local charge balance unit 2 can only be occupied with the trivalent Ga³⁺ ion. The Ga³⁺ position was refined with high precision (±5 pm), and the resulting polyhedron is a GaO₅ square pyramid. The pyramids form densely occupied columns parallel to the twin axis [21¯1¯0]. The analysis of the TB structure yields a fractional occupancy of the boundary plane by Ga of 0.5, which is in good agreement with the result of the chemical composition measurement with energy filtered TEM.     

On Universality of Local Edge Regime for the Deformed Gaussian Unitary Ensemble

We consider the deformed Gaussian ensemble H_n=H_n⁽⁰⁾+M_nH_{n}=H_{n}^{(0)}+M_{n} in which H_n⁽⁰⁾H_{n}^{(0)} is a hermitian matrix (possibly random) and M _n is the Gaussian unitary random matrix (GUE) independent of H_n⁽⁰⁾H_{n}^{(0)}. Assuming that the Normalized Counting Measure of H_n⁽⁰⁾H_{n}^{(0)} converges weakly (in probability if random) to a non-random measure N ⁽⁰⁾ with a bounded support and assuming some conditions on the convergence rate, we prove the universality of the local eigenvalue statistics near the edge of the limiting spectrum of H _n .     

Surface modification, martensitic transformation, and optical properties of hydrogenated ZrO2 nanocondensates via pulsed laser ablation in water

Pulsed laser ablation on Zr plate in water under Q-switch mode and a fluence of 700 and 800 mJ/pulse for a rather high power density of 1.5 and 1.7 × 10¹¹ W/cm², respectively, was employed to fabricate hydrogenated ZrO₂ nanocondensates. X-ray diffraction and transmission electron microscopic observations indicated such nanocondensates are full of {111} and {100} facets and predominantly in monoclinic (m-) rather than cubic- and/or tetragonal (t-) crystal symmetry in particular when fabricated at 700 mJ/pulse. The hydrogenated ZrO₂ nanocondensates underwent martensitic t ?? m transformation at a rather small critical size (ca. 20 nm) due to H⁺ signature and hence oxygen vacancy deficiency in the lattice. The resultant m-phase was free of twin and fault due to site saturation and rather limited growth of the nanosized particles. Spectroscopic characterizations indicated that the nanocondensates have a significant internal compressive stress, (H⁺, Zr²⁺, Zr³⁺) co-signature and hence a smaller band gap of 5.2?C5.3 eV for potential applications in UV region.     

Preparation and mechanism investigation of highly sensitive humidity sensor based on Ag/TiO2

In this paper, a high-performance silver-doped titanium dioxide (Ag/TiO₂) humidity sensor was synthesized using a hydrothermal synthesis method for respiratory monitoring. The sensing mechanism was studied by the first principles of density functional theory (DFT). Calculations show that the doping of Ag⁺ ions increases the adsorption energy of TiO₂ to water molecules. Furthermore, the Ti–O bond in TiO₂ is broken due to the doping of Ag⁺ ions, which promotes the generation of Ti³⁺ defects. Experiments show that the doping of Ag⁺ ions can increase the hydroxide groups, Ti³⁺ defects and oxygen vacancies on the surface of TiO₂, thus effectively improving the responsivity, linearity and hysteresis of the TiO₂ humidity sensor. Compared to TiO₂, the resistance of the Ag/TiO₂ (0.5 mM) humidity sensor reaches 4.5 orders of magnitude with a high response of 39707.1, maximum hysteresis rate of 4.6%, response/recovery time of 31 s/15 s and the best linearity in a range of 11%–95% RH. In addition, the Ag/TiO₂ humidity sensor has been successfully used to detect different modes of respiration and determine the respiratory rate under different respiratory states. Significantly, this work demonstrates potential application value in human healthcare and activities monitoring.     

Exponential lower bounds to solutions of the Schrödinger equation: Lower bounds for the spherical average

For a large class of generalizedN-body-Schrödinger operators,H, we show that ifE<Σ=infσ_ess(H) and ψ is an eigenfunction ofH with eigenvalueE, then $$\begin{array}{*{20}c} {\lim } \\ {R \to \infty } \\ \end{array} R^{ - 1} \ln \left( {\int\limits_{S^{n - 1} } {|\psi (R\omega )|} ^2 d\omega } \right)^{1/2} = - \alpha _0 ,$$ with α ₀ ² +E a threshold. Similar results are given forE≧Σ.     

Measurement of QED structure functions of the photon using azimuthal correlations at LEP

We have studied azimuthal correlations in singly-tagged e⁺e^? → e⁺e^?μ⁺μ^? events at an average Q ² of 5.2 GeV². The data were taken with the OPAL detector at LEP at e⁺e^? centre-of-mass energies close to the Z⁰ mass, with an integrated luminosity of approximately 100 pb^?1. The azimuthal correlations are used to extract the ratio $F_{B}^{αmma}/F_{2}^{αmma}$ of the QED structure functions $F_{B}^{αmma}(x,Q^{2})$ and $F_{2}^{αmma}(x,Q^{2})$ of the photon. In leading order and neglecting the muon mass $F_{B}^{αmma}$ is expected to be identical to the longitudinal structure function $F_{L}^{αmma}$. The measurement of $F_{B}^{αmma}/F_{2}^{αmma}$ is found to be significantly different from zero and to be consistent with the QED prediction.     

Structure of rutile TiO2 (1 1 0) in water and 1 molal Rb at pH 12: Inter-relationship among surface charge, interfacial hydration structure, and substrate structural displacements

The rutile (1 1 0)-aqueous solution interface structure was measured in deionized water (DIW) and 1 molal (m) RbCl + RbOH solution (pH 12) at 25 °C with the X-ray crystal truncation rod method. The rutile surface in both solutions consists of a stoichiometric (1 × 1) surface unit mesh with the surface terminated by bridging oxygen (BO) and terminal oxygen (TO) sites, with a mixture of water molecules and hydroxyl groups (OH⁻) occupying the TO sites. An additional hydration layer is observed above the TO site, with three distinct water adsorption sites each having well-defined vertical and lateral locations. Rb⁺ specifically adsorbs at the tetradentate site between the TO and BO sites, replacing one of the adsorbed water molecules at the interface. There is no further ordered water structure observed above the hydration layer. Structural displacements of atoms at the oxide surface are sensitive to the solution composition. Ti atom displacements from their bulk lattice positions, as large as 0.05 Å at the rutile (1 1 0)-DIW interface, decay in magnitude into the crystal with significant relaxations that are observable down to the fourth Ti-layer below the surface. A systematic outward shift was observed for Ti atom locations below the BO rows, while a systematic inward displacement was found for Ti atoms below the TO rows. The Ti displacements were mostly reduced in contact with the RbCl solution at pH 12, with no statistically significant relaxations in the fourth layer Ti atoms. The distance between the surface 5-fold Ti atoms and the oxygen atoms of the TO site is 2.13 ± 0.03 Å in DIW and 2.05 ± 0.03 Å in the Rb⁺ solution, suggesting molecular adsorption of water at the TO site to the rutile (1 1 0) surface in DIW, while at pH 12, adsorption at the TO site is primarily in the form of an adsorbed hydroxyl group.     

Combined constraints on modified Chaplygin gas model from cosmological observed data: Markov Chain Monte Carlo approach

We use the Markov Chain Monte Carlo method to investigate a global constraints on the modified Chaplygin gas (MCG) model as the unification of dark matter and dark energy from the latest observational data: the Union2 dataset of type supernovae Ia (SNIa), the observational Hubble data (OHD), the cluster X-ray gas mass fraction, the baryon acoustic oscillation (BAO), and the cosmic microwave background (CMB) data. In a flat universe, the constraint results for MCG model are, W_bh² = 0.02263^+0.00184_-0.00162 (1s)^+0.00213_-0.00195 (2s){\Omega_{b}h^{2}\,{=}\,0.02263^{+0.00184}_{-0.00162} (1\sigma)^{+0.00213}_{-0.00195} (2\sigma)}, B_s = 0.7788^+0.0736_-0.0723(1s)^+0.0918_-0.0904 (2s){B_{s}\,{=}\,0.7788^{+0.0736}_{-0.0723}(1\sigma)^{+0.0918}_{-0.0904} (2\sigma)}, a = 0.1079^+0.3397_-0.2539 (1s)^+0.4678_-0.2911 (2s){\alpha\,{=}\,0.1079^{+0.3397}_{-0.2539} (1\sigma)^{+0.4678}_{-0.2911} (2\sigma)}, B = 0.00189^+0.00583_-0.00756(1s)^+0.00660_-0.00915 (2s){B\,{=}\,0.00189^{+0.00583}_{-0.00756}(1\sigma)^{+0.00660}_{-0.00915} (2\sigma)}, and H₀=70.711^+4.188_-3.142 (1s)^+5.281_-4.149(2s){H_{0}=70.711^{+4.188}_{-3.142} (1\sigma)^{+5.281}_{-4.149}(2\sigma)}.     

Etude spectrale d'une famille d'opérateurs non-symétriques intervenant dans la théorie des champs de reggeons

In this paper, we study a few spectral properties of a non-symmetrical operator arising in the Gribov theory. The first and second section are devoted to Bargmann's representation and the study of general spectral properties of the operator: $$\begin{gathered} H_{\lambda ',\mu ,\lambda ,\alpha } = \lambda '\sum\limits_{j = 1}^N {A_j^{ * 2} A_j^2 + \mu \sum\limits_{j = 1}^N {A_j^ * A_j + i\lambda \sum\limits_{j = 1}^N {A_j^ * (A_j + A_j^ * )A_j } } } \hfill \\ + \alpha \sum\limits_{j = 1}^{N - 1} {(A_{j + 1}^ * A_j + A_j^ * A_{j + 1} ),} \hfill \\ \end{gathered}$$ whereA* _j andA _j ,j∈[1,N] are the creation and annihilation operators. In the third section, we restrict our study to the case of nul transverse dimension (N=1). Following the study done in [1], we consider the operator: $$H_{\lambda ',\mu ,\lambda } = \lambda 'A^{ * 2} A^2 + \mu A^ * A + i\lambda A^ * (A + A^ * )A,$$ whereA* andA are the creation and annihilation operators. For λ′>0 and λ′²≦μλ′+λ². We prove that the solutions of the equationu′(t)+H _{λ′, μ,λ} u(t)=0 are expandable in series of the eigenvectors ofH _λ′,μ,λ fort>0. In the last section, we show that the smallest eigenvalue σ(α) of the operatorH _{λ′,μ,λ,α} is analytic in α, and thus admits an expansion: σ(α)=σ₀+ασ₁+α²σ₂+..., where σ₀ is the smallest eigenvalue of the operatorH _{λ′,μ,λ,0}.     

Measurement of the masses and lifetimes of the charmed mesonsD 0,D + andD s +

We present the final results on the measurement of the masses and lifetimes of the mesonsD ⁰,D ⁺ andD _s ⁺ in the NA32 experiment at the CERN SPS, using silicon microstrip detectors and charge-coupled devices for vertex reconstruction. We measure the following lifetimes: \(\tau _{D^0 } = 3.88 \pm _{0.21}^{0.23} \cdot 10^{ - 13} s\) using a sample of 479D°→K ^?π⁺π^?π⁺ and 162D°→K ^?π⁺ decays; \(\tau _{D^ + } = 10.5 \pm _{0.72}^{0.77} \cdot 10^{ - 13} s\) with a sample of 317D ⁺→K ^?π⁺π⁺ decays; \(\tau _{D_s^ + } = 4.69 \pm _{0.86}^{1.02} \cdot 10^{ - 13} s\) with a sample of 54D _s ⁺ →K ⁺ K ^?π⁺ decays. We measure the following masses:m _D ⁰=1864.6±0.3±1.0 MeV,m _D ⁺=1870.0±0.5±1.0 MeV and \(m_{D_s^ + } \) =1967.0±1.0±1.0 MeV.     

Cluster generation under pulsed laser ablation of zinc oxide

Neutral and cationic Zn _n O _m clusters of various stoichiometry have been produced by nanosecond laser ablation of ZnO in vacuum and investigated by time-of-flight mass spectrometry. Particular attention was paid to the effect of laser wavelength (in the range from near-IR to UV) on cluster composition. Under 193-nm laser ablation, the charged clusters are essentially substoichiometric with Zn_nO_n-1⁺\mathrm{Zn}_{n}\mathrm{O}_{n-1}^{+} and Zn_nO_n-3⁺\mathrm{Zn}_{n}\mathrm{O}_{n-3}^{+} being the most abundant series. Both sub- and stoichiometric cationic clusters are generated in abundance at 532- and 1064-nm ablation whose composition depends on the cluster size. The reactivity of small stoichiometric Zn_nO_n⁺\mathrm{Zn}_{n}\mathrm{O}_{n}^{+} clusters (n<11) toward hydrogen is found to be high, while oxygen-deficient species are less reactive. The neutral plume particles are mainly stoichiometric with Zn₄O₄ tetramer being a magic cluster. It is suggested that the Zn₄O₄ loss is the dominant fragmentation channel of large zinc oxide clusters upon electron impact. Plume expansion conditions under ZnO ablation with visible and IR laser pulses are shown to be favorable for stoichiometric cluster formation.     

The effect of water vapor on the electrical properties and sensitivity of thin-film gas sensors based on tin dioxide

The results of theoretical and experimental studies into the effect of water vapor on the electrical conductance of a gas sensor and the sensor response to hydrogen action are discussed. A relation describing the dependence of electrical conductance G₀ on absolute humidity in the pure air is derived using a hypothesis of the presence of space-charge regions depleted of electrons between the SnO ₂ grains in a polycrystalline tin dioxide film. Due to dissociative chemisorption of water molecules, the energy-band bending at the SnO ₂ grain interfaces decreases and the oxygen-vacancy concentration in the grains increases, resuling in an increase in G₀. An equation for the sensor response to hydrogen action is derived (the G₁/G₀, ratio, where G₁ is the sensor conductance in a gas mixture containing molecular hydrogen). The expression describes the dependence of G₁/G₀ on the hydrogen concentration in the interval 50–6·10³ ppm, band bending at the SnO ₂ grain interface, and sensor temperature. The dependences of the sensor conductance, highest possible conductance, and energy-band bending on temperature and absolute humidity resulting from processing of the experimental data are in good agreement with the theoretical predictions. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 50–56, August, 2008.