The effect of flexoelectricity on the dielectric properties of inhomogeneously strained ferroelectric thin films

Recent experimental measurements of large flexoelectric coefficients in ferroelectric ceramics suggest that strain gradients can affect the polarization and permittivity behaviour of inhomogeneously strained ferroelectrics. Here we present a phenomenological model of the effect of flexoelectricity on the dielectric constant, polarization, Curie temperature (T-C), temperature of maximum dielectric constant (T-m) and temperature of the onset of reversible polarization (T-ferro) for ferroelectric thin films subject to substrate-induced epitaxial strains that are allowed to relax with thickness, and the qualitative and quantitative predictions of the model are compared with experimental results for (Ba0.5Sr0.5)TiO3 thin films on SrRuO3 electrodes. It is shown that flexoelectricity can play an important role in decreasing the maximum dielectric constant of ferroelectric thin films under inhomogeneous in-plane strain, regardless of the sign of the strain gradient.

Reduced-size polarized basis sets for calculations of molecular electric properties. III. Second-row atoms

Reduced-size polarized (ZmPolX) basis sets are developed for the second-row atoms X = Si, P, S, and Cl. The generation of these basis sets follows from a simple physical model of the polarization effect of the external electric field which leads to highly compact polarization functions to be added to the chosen initial basis set. The performance of the ZmPolX sets has been investigated in calculations of molecular dipole moments and polarizabilities. Only a small deterioration of the quality of the calculated molecular electric properties has been found. Simultaneously the size of the present reduced-size ZmPolX basis sets is about one-third smaller than that of the usual polarized (PolX) sets. This reduction considerably widens the range of applications of the ZmPolX sets in calculations of molecular dipole moments, dipole polarizabilities, and related properties.

Spin-Polarization Mechanisms of the Nitrogen-Vacancy Center in Diamond

The nitrogen-vacancy (NV) center in diamond has shown great promise for quantum information due to the ease of initializing the qubit and of reading out its state. Here we show the leading mechanism for these effects gives results opposite from experiment; instead both must rely on new physics. Furthermore, NV centers fabricated in nanometer-sized diamond clusters are stable, motivating a bottom-up qubit approach, with the possibility of quite different optical properties to bulk.

Large-scale density functional calculations of the surface properties of the Wigner crystal

The surface properties of the jellium model have been investigated by large supercell computations in the density functional theory-local spin-density (DFT-LSD) approach for planar slabs with up to 1000 electrons. A wide interval of densities has been explored, extending into the stability range of the Wigner crystal. Most computations have been carried out on nominally paramagnetic samples with an equal number of spin-up and spin-down electrons. The results show that within DFT-LSD spontaneous spin polarization and charge localization start nearly simultaneously at the surface for r(s) similar to 20, then, with decreasing density, they progress toward the center of the slab. Electrons are fully localized and spin polarized at r(s) = 30. At this density the charge distribution is the superposition of disjoint charge blobs, each corresponding to one electron. The distribution of blobs displays both regularities and disorder, the first being represented by well-defined planes and simple in-plane geometries, and the latter by a variety of surface defects. The surface energy, surface dipole, electric polarisability, and magnetization pattern have been determined as a function of density. All these quantities display characteristic anomalies at the density of the localization transition. The analysis of the low-frequency electric conductivity shows that in the fluid paramagnetic regime the in-plane current preferentially flows in the central region of the slab and the two spin channels are equally conducting. In the charge localized, spin-polarized regime, conductivity is primarily a surface effect, and an apparent asymmetry is observed in the two spin currents.

Stability of dust lattice modes in the presence of charged dust grain polarization in plasmas

We discuss the effect of the attractive force associated with overlapping Debye spheres on the dispersion properties of the longitudinal and transverse dust lattice waves in strongly coupled dust crystals. The dust grain attraction is shown to contribute to a destabilization of the longitudinal dust lattice oscillations. The (optic-like) transverse mode dispersion law is shown to change. due to the Debye sphere dressing effect, from the known inverse-dispersive ("backward wave") form into a normal dispersive law (i.e. the group velocity changes sign). The stability of one-dimensionless bi-layers, consisting of (alternating) negatively and positively charged dust particles, is also discussed. The range of parameter values (mainly in terms of the lattice parameter kappa) where the above predictions are valid, are presented. (c) 2005 Elsevier B.V. All rights reserved.

Epitaxial strain and electric boundary condition effects on the structural and ferroelectric properties of BiFeO3 films

The influence of both compressive and tensile epitaxial strain along with the electrical boundary conditions on the ferroelastic and ferroelectric domain patterns of bismuth ferrite films was studied. BiFeO3 films were grown on SrTiO3(001), DyScO3(110), GdScO3(110), and SmScO3(110) substrates to investigate the effect of room temperature in-plane strain ranging from -1.4% to +0.75%. Piezoresponse force microscopy, transmission electron microscopy, x-ray diffraction measurements, and ferroelectric polarization measurements were performed to study the properties of the films. We show that BiFeO3 films with and without SrRuO3 bottom electrode have different growth mechanisms and that in both cases reduction of the domain variants is possible. Without SrRuO3, stripe domains with reduced variants are formed on all rare earth scandate substrates because of their monoclinic symmetry. In addition, tensile strained films exhibit a rotation of the unit cell with increasing film thickness. On the other side, the presence of SrRuO3 promotes step flow growth of BiFeO3. In case of vicinal SrTiO3 and DyScO3 substrates with high quality SrRuO3 bottom electrode and a low miscut angle of approximate to 0.15 degrees we observed suppression of the formation of certain domain variants. The quite large in-plane misfit of SrRuO3 with GdScO3 and SmScO3 prevents the growth of high quality SrRuO3 films and subsequent domain variants reduction in BiFeO3 on these substrates, when SrRuO3 is used as a bottom electrode.

INFLUENCE OF CORE POLARIZATION ON THE ELECTRON-AFFINITY OF CA

We have developed a method, based on the use of B-spline basis sets and model potentials, for determining properties of systems with two or three electrons outside a polarizable closed-shell core. It is applied to the calculation of the electron affinity of Ca and the resulting value of 17.7 meV is in excellent agreement with the most recent experiments. It is found that the dielectronic core-valence interaction reduces the electron affinity by 39.5 meV.

STO and GTO field-induced polarization functions for H to Kr

Field-induced polarization (FIP) functions were proposed over two decades ago to improve the accuracy of calculated response properties, and the FIP functions in GTO form for H and C to F were tested on small molecules, with encouraging results. The concept of FIP,is now extended to all atoms up to Kr. New simplifying approximations for the description of asymptotic highest occupied atomic orbitals. (HOAOs) are introduced in this study. They provide the basis for STO and GTO exponents of a complete set of FIP functions from H to Kr, which are both listed for the convenience of the users. Tests on the polarizabilities of a series of atoms and molecules demonstrate that addition of the FIP basis functions to a series' of standard basis sets drastically improves the performance of all these basis sets compared to converged results. Moreover, the byproduct of this study (approximate asymptotic HOAOs) provides information for the construction of accurate basis sets for long-range ground state properties. (C) 2003 Wiley Periodicals, Inc.

Quantum chemistry studies on electronic properties of CN adsorbed on silver electrodes

The electronic properties of CN adsorbed on Ag electrodes at different potentials have been studied by using the method of self-consistent-charge discrete variational Xa (SCC-DV-Xa) cluster calculations. It is shown that the binding of NCAg is dominated by both electrostatic and polarization effects derived from the charge of CN, and that the transfer of s charge from CN to silver is the largest donation contribution. The electrode potential influences this charge transfer process and the interaction between CN adsorbate and silver electrode. The results of quantum chemistry calculations fit well with the experimental data of in situ spectroscopic studies on the CN/Ag electrode systems. © 1991.

Fabrication and optical properties of gold nanotube arrays

Arrays of gold nanotubes with polypyrrole cores were grown on glass substrates by electrodeposition into thin film porous alumina templates. Measurements of optical transmission revealed strong extinction peaks related to plasmonic resonances, which were sensitive to the polarization state and angle of incidence. On prolonging the electrodeposition of gold, the polypyrrole core became fully encapsulated and this had a dramatic effect on the optical properties of the arrays, which was rationalized by finite element simulation of the local field intensities resulting from plasmon excitation.

Influence of the interfacing with an electrically inhomogeneous bottom electrode on the ferroelectric properties of epitaxial PbTiO3

The influence of an electrically inhomogeneous epitaxial bottom layer on the ferroelectric and electrical properties has been explored in epitaxial PbTiO3 (PTO)/La0.7Sr0.3MnO3 (LSMO) submicron structures using atomic force microscopy. The submicron LSMO-dot structures underneath the ferroelectric PTO film allow exploring gradual changes in material properties. The LSMO interfacial layer influences significantly both electrical and ferroelectric properties of the upper PTO layer. The obtained results show that the as-grown polarization state of an epitaxial ferroelectric layer is strongly influenced by the properties of the layer on top of which it is deposited. (C) 2013 AIP Publishing LLC.

Piezoelectric properties of PbTiO(3) thin films characterized with piezoresponse force and high resolution transmission electron microscopy

In this paper we investigate the piezoelectric properties of PbTiO(3) thin films grown by pulsed laser deposition with piezoresponse force microscopy and transmission electron microscopy. The as-grown films exhibit an upward polarization, inhomogeneous distribution of piezoelectric characteristics concerning local coercive fields, and piezoelectric coefficient. In fact, the data obtained reveal imprints during piezoresponse force microscopy measurements, nonlinearity in the piezoelectric deformation, and limited polarization reversal. Moreover, transmission electron microscopy shows the presence of defects near the film/substrate interface, which can be associated with the variations of piezoelectric properties.

Relativistic breather-type solitary waves with linear polarization in cold plasmas

Linearly polarized solitary waves, arising from the interaction of an intense laser pulse with a plasma, are investigated. Localized structures, in the form of exact numerical nonlinear solutions of the one-dimensional Maxwell-fluid model for a cold plasma with fixed ions, are presented. Unlike stationary circularly polarized solitary waves, the linear polarization gives rise to a breather-type behavior and a periodic exchange of electromagnetic energy and electron kinetic energy at twice the frequency of the wave. A numerical method based on a finite-differences scheme allows us to compute a branch of solutions within the frequency range Ωmin<Ω<ωpe, where ωpe and Ωmin are the electron plasma frequency and the frequency value for which the plasma density vanishes locally, respectively. A detailed description of the spatiotemporal structure of the waves and their main properties as a function of Ω is presented. Small-amplitude oscillations appearing in the tail of the solitary waves, a consequence of the linear polarization and harmonic excitation, are explained with the aid of the Akhiezer-Polovin system. Direct numerical simulations of the Maxwell-fluid model show that these solitary waves propagate without change for a long time.

Resistivity and Induced Polarization Monitoring of Biogas combined with Microbial Ecology on a Brown field Site

The accumulation of biogenic greenhouse gases (methane, carbon dioxide) in organic sediments is an important factor in the redevelopment and risk management of many brownfield sites. Good practice with brownfield site characterization requires the identification of free-gas phases and pathways that allow its migration and release at the ground surface. Gas pockets trapped in the subsurface have contrasting properties with the surrounding porous media that favor their detection using geophysical methods. We have developed a case study in which pockets of gas were intercepted with multilevel monitoring wells, and their lateral continuity was monitored over time using resistivity. We have developed a novel interpretation procedure based on Archie’s law to evaluate changes in water and gas content with respect to a mean background medium. We have used induced polarization data to account for errors in applying Archie’s law due to the contribution of surface conductivity effects. Mosaics defined by changes in water saturation allowed the recognition of gas migration and groundwater infiltration routes and the association of gas and groundwater fluxes. The inference on flux patterns was analyzed by taking into account pressure measurements in trapped gas reservoirs and by metagenomic analysis of the microbiological content, which was retrieved from suspended sediments in groundwater sampled in multilevel monitoring wells. A conceptual model combining physical and microbiological subsurface processes suggested that biogas trapped at depth may have the ability to quickly travel to the surface.

Measurement and modeling of hyperfine properties in ferroic materials

This thesis presents the results of perturbed angular correlation (PAC) experiments , an experimental technique which measures the hyperfine interaction at probes (radioactive ions implanted in the materials to study), from which one infers local information on an atomic scale. Furthermore, abinitio calculations using density functional theory electronic obtain results that directly complement the experiments, and are also used for theoretical research. These methods were applied in two families of materials. The manganites, with the possible existence of magnetic, charge, orbital and ferroelectric orders, are of fundamental and technological interest. The experimental results are obtained in the alkaline-earth manganites (Ca, Ba, Sr), with special interest due to the structural variety of possible polymorphs. With probes of Cd and In the stability of the probe and its location in a wide temperature range is established and a comparison with calculations allows the physical interpretation of the results. Calculations of hyperfine properties in rare-earth manganites are also presented. The second type of materials in which hyperfine properties were studied are the Manganese pnictides: MnAs, MnSb, and MnBi, compounds in which magnetism is fundamental. The experimental results obtained mainly consider the MnAs compound, whose magneto-structural transition is of great interest. The transition is analyzed in detail with the local resolution characteristic of the technique, obtaining information of the character of the transition also with complementary, more conventional techniques. The last work in this thesis uses only the first principles calculations, continuing the theme of the hyperfine interactions, but this time with respect to ferroelectrics. Several transition metal oxides with perovskite or distorted structures are considered. The electric field gradient which exists due to the quadrupole interaction in nuclei is related to the spontaneous electric polarization, the main quantity measured in ferroelectrics. This study provides a fundamental theoretical basis for previous empirical studies, suggesting new directions for research in ferroelectrics and multiferroics using techniques which measure the electric field gradient.