Anomalous temperature dependence of phonons and photoluminescence bands in pyrochlore Er(2)Ti(2)O(7): signatures of structural deformation at 130 K

We report a Raman study of single crystal pyrochlore Er(2)Ti(2)O(7) as a function of temperature from 12 to 300 K. In addition to the phonons, various photoluminescence (PL) lines of Er(3+) in the visible range are also observed. Our Raman data show an anomalous red-shift of two phonons (one at similar to 200 cm(-1) and another at similar to 520 cm(-1)) upon cooling from room temperature which is attributed to phonon-phonon anharmonic interactions. However, the phonons at similar to 310, 330, and 690 cm(-1) initially show a blue-shift upon cooling from room temperature down to about 130 K, followed by a red-shift, indicating a structural deformation at similar to 130 K. The intensities of the PL bands associated with the transitions between the various levels of the ground state manifold ((4)I(15/2)) and the (2)H(11/2) as well as (4)S(3/2) excited state manifolds of Er(3+) show a change at similar to 130 K. Moreover, the temperature dependence of the peak position of the two PL bands shows a change in their slope (d(omega)/d(T)) at similar to 130 K, thus further strengthening the proposal of a structural deformation. The temperature dependence of the peak positions of the PL bands has been analyzed using the theory of optical dephasing in crystals.

Structural and dielectric behavior of pulsed laser ablated Sr(0.6)Ca(0.4)TiO(3) thin film and asymmetric multilayer of SrTiO(3) and CaTiO(3)

Homogeneous thin films of Sr(0.6)Ca(0.4)TiO(3) (SCT40) and asymmetric multilayer of SrTiO(3) (STO) and CaTiO(3) (CTO) were fabricated on Pt/Ti/SiO(2)/Si substrates by using pulsed laser deposition technique. The electrical behavior of films was observed within a temperature range of 153 K-373 K. A feeble dielectric peak of SCT40 thin film at 273 K is justified as paraelectric to antiferroelectric phase transition. Moreover, the Curie-Weiss temperature, determined from the epsilon'(T) data above the transition temperature is found to be negative. Using Landau theory, the negative Curie-Weiss temperature is interpreted in terms of an antiferroelectric transition. The asymmetric multilayer exhibits a broad dielectric peak at 273 K. and is attributed to interdiffusion at several interfaces of multilayer. The average dielectric constants for homogeneous Sr(0.6)Ca(0.4)TiO(3) films (similar to 650) and asymmetric multilayered films (similar to 350) at room temperature are recognized as a consequence of grain size effect. Small frequency dispersion in the real part of the dielectric constants and relatively low dielectric losses for both cases ensure high quality of the films applicable for next generation integrated devices. (C) 2011 Elsevier B.V. All rights reserved.

A Refined Methodology for Durability-Based Service Life Estimation of Reinforced Concrete Structural Elements Considering Fuzzy and Random Uncertainties

A reliable method for service life estimation of the structural element is a prerequisite for service life design. A new methodology for durability-based service life estimation of reinforced concrete flexural elements with respect to chloride-induced corrosion of reinforcement is proposed. The methodology takes into consideration the fuzzy and random uncertainties associated with the variables involved in service life estimation by using a hybrid method combining the vertex method of fuzzy set theory with Monte Carlo simulation technique. It is also shown how to determine the bounds for characteristic value of failure probability from the resulting fuzzy set for failure probability with minimal computational effort. Using the methodology, the bounds for the characteristic value of failure probability for a reinforced concrete T-beam bridge girder has been determined. The service life of the structural element is determined by comparing the upper bound of characteristic value of failure probability with the target failure probability. The methodology will be useful for durability-based service life design and also for making decisions regarding in-service inspections.

New nine-node Lagrangian quadrilateral plate element based on Mindlin-Reissner theory using IFM

This paper presents a new nine-node Lagrangian quadrilateral plate bending element (MQP9) using the Integrated Force Method (IFM) for the analysis of thin and moderately thick plate bending problems. Three degrees of freedom: transverse displacement w and two rotations theta(x) and theta(y) are considered at each node of the element. The Mindlin-Reissner theory has been employed in the formulation which accounts the effect of shear deformation. Many standard plate bending benchmark problems have been analyzed using the new element MQP9 for various grid sizes via Integrated Force Method to estimate defections and bending moments. These results of the new element MQP9 are compared with those of similar displacement-based plate bending elements available in the literature. The results are also compared with exact solutions. It is observed that the presented new element MQP9 is free from shear locking and produced, in general, excellent results in all plate bending benchmark problems considered.

A finite population model of mlecular evolution: theory and computation

This article is concerned with the evolution of haploid organisms that reproduce asexually. In a seminal piece of work, Eigen and coauthors proposed the quasispecies model in an attempt to understand such an evolutionary process. Their work has impacted antiviral treatment and vaccine design strategies. Yet, predictions of the quasispecies model are at best viewed as a guideline, primarily because it assumes an infinite population size, whereas realistic population sizes can be quite small. In this paper we consider a population genetics-based model aimed at understanding the evolution of such organisms with finite population sizes and present a rigorous study of the convergence and computational issues that arise therein. Our first result is structural and shows that, at any time during the evolution, as the population size tends to infinity, the distribution of genomes predicted by our model converges to that predicted by the quasispecies model. This justifies the continued use of the quasispecies model to derive guidelines for intervention. While the stationary state in the quasispecies model is readily obtained, due to the explosion of the state space in our model, exact computations are prohibitive. Our second set of results are computational in nature and address this issue. We derive conditions on the parameters of evolution under which our stochastic model mixes rapidly. Further, for a class of widely used fitness landscapes we give a fast deterministic algorithm which computes the stationary distribution of our model. These computational tools are expected to serve as a framework for the modeling of strategies for the deployment of mutagenic drugs.

Mechanistic Aspects for the Formation of Copper Dimer Bridged by Phosphonic Acid and Extending Its Dimensionality by Organic and Inorganic Linkers: Synthesis, Structural Characterization, Magnetic Properties, and Theoretical Studies

Six new copper metal complexes with formulas Cu(H2O)(2,2'-bpy) (H2L)](2) center dot H4L center dot 4 H2O (1), {Cu(H2O)(2,2'-bpy)-(H3L)}(2)(H2L)]center dot 2H(2)O (2), Cu(H2O)(1,10-phen)(H2L)](2)center dot 6H(2)O (3), Cu(2,2'-bpy)(H2L)](n)center dot nH(2)O (4), Cu(1,10-phen)(H2L)](n)center dot 3nH(2)O (5), and {Cu(2,2'-bpy)(MoO3)}(2)(L)](n)center dot 2nH(2)O (6) have been synthesized starting from p-xylylenediphosphonic acid (H4L) and 2,2'-bipyridine (2,2'-bpy) or 1,10-phenanthroline (1,10-phen) as secondary linkers and characterized by single crystal X-ray diffraction analysis, IR spectroscopy, and thermogravimetric (TG) analysis. All the complexes were synthesized by hydrothermal methods. A dinuclear motif (Cu-dimer) bridged by phosphonic acid represents a new class of simple building unit (SBU) in the construction of coordination architectures in metal phosphonate chemistry. The initial pH of the reaction mixture induced by the secondary linker plays an important role in the formation of the molecular phosphonates 1, 2, and 3. Temperature dependent hydrothermal synthesis of the compounds 1, 2, and 3 reveals the mechanism of the self assembly of the compounds based on the solubility of the phosphonic acid H4L. Two-dimensional coordination polymers 4, 5, and 6, which are formed by increasing the pH of the reaction mixture, comprise Cu-dimers as nodes, organic (H2L) and inorganic (Mo4O12) ligands as linkers. The void space-areas, created by the (4,4) connected nets in compounds 4 and 5, are occupied by lattice water molecules. Thus compounds 4 and 5 have the potential to accommodate guest species/molecules. Variable temperature magnetic studies of the compounds 3, 4, 5, and 6 reveal the antiferromagnetic interactions between the two Cu(II) ions in the eight membered ring, observed in their crystal structures. A density functional theory (DFT) calculation correlates the conformation of the Cu-dimer ring with the magnitude of the exchange parameter based on the torsion angle of the conformation.

Pressure induced structural phase transformation in TiN: a first-principles study

Titanium nitride (TiN), which is widely used for hard coatings, reportedly undergoes a pressure-induced structural phase transformation, from a NaCl to a CsCl structure, at similar to 7 GPa. In this paper, we use first-principles calculations based on density functional theory with a generalized gradient approximation of the exchange correlation energy to determine the structural stability of this transformation. Our results show that the stress required for this structural transformation is substantially lower (by more than an order of magnitude) when it is deviatoric in nature vis-a-vis that under hydrostatic pressure. Local stability of the structure is assessed with phonon dispersion determined at different pressures, and we find that CsCl structure of TiN is expected to distort after the transformation. From the electronic structure calculations, we estimate the electrical conductivity of TiN in the CsCl structure to be about 5 times of that in NaCl structure, which should be observable experimentally. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4798591]

Structural, electrical and dielectric properties of sputtered TiO2 films for Al/TiO2/Si capacitors

Metal-oxide semiconductor capacitors based on titanium dioxide (TiO2) gate dielectrics were prepared by RF magnetron sputtering technique. The deposited films were post-annealed at temperatures in the range 773-1173 K in air for 1 hour. The effect of annealing temperature on the structural properties of TiO2 films was investigated by X-ray diffraction and Raman spectroscopy, the surface morphology was studied by atomic force microscopy (AFM) and the electrical properties of Al/TiO2/p-Si structure were measured recording capacitance-voltage and current-voltage characteristics. The as-deposited films and the films annealed at temperatures lower than 773 K formed in the anatase phase, while those annealed at temperatures higher than 973 K were made of mixtures of the rutile and anatase phases. FTIR analysis revealed that, in the case of films annealed at 1173 K, an interfacial layer had formed, thereby reducing the dielectric constant. The dielectric constant of the as-deposited films was 14 and increased from 25 to 50 with increases in the annealing temperature from 773 to 973 K. The leakage current density of as-deposited films was 1.7 x 10(-5) and decreased from 4.7 X 10(-6) to 3.5 x 10(-9) A/cm(2) with increases in the annealing temperature from 773 to 1173 K. The electrical conduction in the Al/TiO2/p-Si structures was studied on the basis of the plots of Schottky emission, Poole-Frenkel emission and Fowler-Nordheim tunnelling. The effect of structural changes on the current-voltage and capacitance-voltage characteristics of Al/TiO2/p-Si capacitors was also discussed.

Asymptotic expansions for the structural wavenumbers of isotropic and orthotropic fluid-filled circular cylindrical shells in the intermediate frequency range

We consider wavenumbers in in vacuo and fluid-filled isotropic and orthotropic shells. Using the Donnell-Mushtari (DM) theory we find compact and elegant asymptotic expansions for the wavenumbers in the intermediate frequency range, i.e., around the ring frequency. This frequency range corresponds to the frequencies where there is a rapid change in the values of bending wavenumbers and is found to exist in isotropic and orthotropic shells (in vacua and fluid-filled) for low circumferential orders n only. The same is first identified using the n=0 mode of an orthotropic shell. Following this, using the expression for the intermediate frequency, asymptotic expansions are found for other cases. Here, in order to get compact expansions we consider slight orthotropy (epsilon << 1) and light fluid loading (mu << 1). Thus, the orthotropy parameter epsilon and the fluid loading parameter mu are used as asymptotic parameters along with the non-dimensional thickness parameter beta. The methodology can be extended to any order of epsilon, only the expansions become unwieldy. The expansions are matched with the numerical solutions of the corresponding dispersion relation. The match is found to be good.

Effect of post-deposition annealing on transverse piezoelectric coefficient and vibration sensing performance of ZnO thin films

The present experimental study investigates the influence of post-deposition annealing on the transverse piezoelectric coefficient (d(31)) value of ZnO thin films deposited on a flexible metal alloy substrate, and its relationship with the vibration sensing performance. Highly c-axis oriented and crystalline ZnO thin films were deposited on flexible Phynox alloy substrate via radio frequency (RF) reactive magnetron sputtering. ZnO thin film samples were annealed at different temperatures ranging from 100 degrees C to 500 degrees C, resulting in the temperature of 300 degrees C determined as the optimum annealing temperature. The crystallinity, morphology, microstructure, and rms surface roughness of annealed ZnO thin films were systematically investigated by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), and Atomic Force Microscopy (AFM), respectively. The piezoelectric d(31) coefficient value was measured by 4-point bending method. ZnO thin film annealed at 300 degrees C was highly c-axis oriented, crystalline, possesses fine surface morphology with uniformity in the grain size. This film showed higher d(31) coefficient value of 7.2 pm V-1. A suitable in-house designed and developed experimental set-up, for evaluating the vibration sensing performance of annealed ZnO thin films is discussed. As expected the ZnO thin film annealed at 300 degrees C showed relatively better result for vibration sensing studies. It generates comparatively higher peak output voltage of 147 mV, due to improved structural and morphological properties, and higher piezoelectric d(31) coefficient value. (C) 2014 Elsevier B. V. All rights reserved.

Structural, Electrical and Magnetic Behaviour of FeTe0.5Se0.5 Superconductor

We report the synthesis as well as structural and physical properties of the bulk polycrystalline FeTe and FeTe0.5Se0.5 compounds. These samples are synthesised by the solid state-reaction method via vacuum encapsulation. Both studied compounds are crystallized in a tetragonal phase with space group P4/nmm. The parent FeTe compound shows an anomaly in resistivity measurement at around 78 K, which is due to the structural change along with a magnetic phase transition. The superconductivity in the FeTe0.5Se0.5 sample at 13 K is confirmed by the resistivity measurements. DC magnetisation along with an isothermal (M-H) loop shows that FeTe0.5Se0.5 possesses bulk superconductivity. The upper critical field is estimated through resistivity rho (T,H) measurements using Gingzburg-Landau (GL) theory and is above 50 T with 50 % resistivity drop criterion. The origin of the resistive transition broadening under magnetic field is investigated by thermally activated flux flow. The magnetic field dependence of the activation energy of the flux motion is discussed.

Anomalous power law decay in solvation dynamics of DNA: a mode coupling theory analysis of ion contribution

Several time dependent fluorescence Stokes shift (TDFSS) experiments have reported a slow power law decay in the hydration dynamics of a DNA molecule. Such a power law has neither been observed in computer simulations nor in some other TDFSS experiments. Here we observe that a slow decay may originate from collective ion contribution because in experiments DNA is immersed in a buffer solution, and also from groove bound water and lastly from DNA dynamics itself. In this work we first express the solvation time correlation function in terms of dynamic structure factors of the solution. We use mode coupling theory to calculate analytically the time dependence of collective ionic contribution. A power law decay in seen to originate from an interplay between long-range probe-ion direct correlation function and ion-ion dynamic structure factor. Although the power law decay is reminiscent of Debye-Falkenhagen effect, yet solvation dynamics is dominated by ion atmosphere relaxation times at longer length scales (small wave number) than in electrolyte friction. We further discuss why this power law may not originate from water motions which have been computed by molecular dynamics simulations. Finally, we propose several experiments to check the prediction of the present theoretical work.

Influence of sputter power on structural and electrical properties of TiO2 films for Al/TiO2/Si gate capacitors

Titanium dioxide (TiO2) thin films were deposited onto p-Si substrates held at room temperature by reactive Direct Current (DC) magnetron sputtering at various sputter powers in the range 80-200W. The as-deposited TiO2 films were annealed at a temperature of 1023K. The post-annealed films were characterized for crystallographic structure, chemical binding configuration, surface morphology and optical absorption. The electrical and dielectric properties of Al/TiO2/p-Si structure were determined from the capacitance-voltage and current-voltage characteristics. X-ray diffraction studies confirmed that the as-deposited films were amorphous in nature. After post-annealing at 1023K, the films formed at lower powers exhibited anatase phase, where as those deposited at sputter powers >160W showed the mixed anatase and rutile phases of TiO2. The surface morphology of the films varied significantly with the increase of sputter power. The electrical and dielectric properties on the air-annealed Al/TiO2/p-Si structures were studied. The effect of sputter power on the electrical and dielectric characteristics of the structure of Al/TiO2/p-Si (metal-insulator-semiconductor) was systematically investigated. Copyright (c) 2014 John Wiley & Sons, Ltd.