Showing papers on "Ferroelectricity published in 2002"

Study of diluted magnetic semiconductor: Co-doped ZnO

Abstract: We report on the high-temperature ferromagnetism in Co-doped ZnO films fabricated by the sol–gel method above 350 K. The lattice constant of c axis of wurtzite Zn1−xCoxO follows Vergard’s law for 0

Ferroelectric Bi3.25La0.75Ti3O12 Films of Uniform a-Axis Orientation on Silicon Substrates

Abstract: The use of bismuth-layered perovskite films for planar-type nonvolatile ferroelectric random-access memories requires films with spontaneous polarization normal to the plane of growth. Epitaxially twinned a axis–oriented La-substituted Bi4Ti3O12 (BLT) thin films whose spontaneous polarization is entirely along the film normal were grown by pulsed laser deposition on yttria-stabilized zirconia-buffered Si(100) substrates using SrRuO3 as bottom electrodes. Even though the (118) orientation competes with the (100) orientation, epitaxial films with almost pure (100) orientation were grown using very thin, strained SrRuO3 electrode layers and kinetic growth conditions, including high growth rates and high oxygen background pressures to facilitate oxygen incorporation into the growing film. Films with the a-axis orientation and having their polarization entirely along the direction normal to the film plane can achieve a remanent polarization of 32 microcoulombs per square centimeter.

Imaging mechanism of piezoresponse force microscopy of ferroelectric surfaces

Abstract: In order to determine the origin of image contrast in piezoresponse force microscopy (PFM), analytical descriptions of the complex interactions between a small tip and ferroelectric surface are derived for several sets of limiting conditions. Image charge calculations are used to determine potential and field distributions at the tip-surface junction between a spherical tip and an anisotropic dielectric half plane. Methods of Hertzian mechanics are used to calculate the response amplitude in the electrostatic regime. In the electromechanical regime, the limits of strong (classical) and weak (field-induced) indentation are established and the relative contributions of electroelastic constants are determined. These results are used to construct ``piezoresponse contrast mechanism maps'' that correlate the imaging conditions with the PFM contrast mechanisms. Conditions for quantitative PFM imaging are set forth. Variable-temperature PFM imaging of domain structures in ${\mathrm{BaTiO}}_{3}$ and the temperature dependence of the piezoresponse are compared with Ginzburg-Devonshire theory. An approach to the simultaneous acquisition of piezoresponse and surface potential images is proposed.

Preparation and Characterization of High Temperature Perovskite Ferroelectrics in the Solid-Solution (1-x)BiScO3–xPbTiO3

Abstract: The dielectric and piezoelectric properties of the new perovskite solid solution system (1-x)BiScO3–xPbTiO3 were investigated. This system is representative of a new group of high temperature piezoelectrics that includes Bi(Me)O3–PbTiO3, where Me+3 is a relatively large cation, Sc, Y, Yb, In, etc., and combinations thereof. In the (1-x)BiScO3–xPbTiO3 series, perovskite stability was achieved for x>50 mol% PbTiO3 being ferroelectric rhombohedral and transforming to ferroelectric tetragonal in the region x=64 mol% PbTiO3, designated as the morphotropic phase boundary (MPB). Analogous to (1-x)PbZrO3–xPbTiO3 (PZT), the dielectric and piezoelectric properties were enhanced for compositions near the MPB. Piezoelectric coefficient d33 values reached 450 pC/N, comparable to soft PZT's with a transition temperature of 450°C, more than 100°C higher than commercial PZT. The combination of high TC and excellent piezoelectric activity make (1-x)BiScO3–xPbTiO3 materials candidates for high temperature, and temperature stable actuators and transducers.

Observation of nanoscale 180 degrees stripe domains in ferroelectric PbTiO3 thin films.

Abstract: We report the observation of periodic 180 degrees stripe domains below the ferroelectric transition in thin films. Epitaxial PbTiO3 films of thickness d=1.6 to 42 nm on SrTiO3 substrates were studied using x-ray scattering. Upon cooling below T(C), satellites appeared around Bragg peaks indicating the presence of 180 degrees stripe domains of period Lambda=3.7 to 24 nm. The dependence of Lambda on d agrees well with theory including epitaxial strain effects, while the suppression of T(C) for thinner films is significantly larger than that expected solely from stripe domains.

Synthesis of Single-Crystalline Perovskite Nanorods Composed of Barium Titanate and Strontium Titanate

Abstract: We report the solution-based synthesis of single-crystalline nanorods composed of barium titanate (BaTiO3) and strontium titanate (SrTiO3), which yields well-isolated nanorods with diameters ranging from 5 to 60 nm and lengths reaching up to >10 μm. Electron microscopy and diffraction measurements show that these nanorods are composed of single-crystalline cubic perovskite BaTiO3 and SrTiO3 with a principal axis of the unit cell preferentially aligned along the wire length. These BaTiO3 and SrTiO3 nanorods should provide promising materials for fundamental investigations on nanoscale ferroelectricity, piezoelectricity, and paraelectricity.

Flexoelectric polarization of barium strontium titanate in the paraelectric state

Abstract: The strain-gradient-induced polarization (flexoelectric effect) was investigated in Ba0.67Sr0.33TiO3 (BST) ceramic at temperatures above the 21 °C Curie point. At 23 °C the flexoelectric coefficient μ12 was more than one order of magnitude greater than the highest value measured in lead magnesium niobate ceramic. Over the temperature range of linear Curie–Weiss behavior, the coefficient μ12 was roughly proportional to the dielectric permittivity; however, the constant of proportionality was higher than predicted for simple ionic solids. The unexpected behavior in the BST ceramic suggests the need for a broader database of flexoelectric coefficients.

Dielectric behavior of three-phase percolative Ni–BaTiO3/polyvinylidene fluoride composites

Abstract: A three-phase percolative composite with a ferroelectric phase (BaTiO3) and metallic inclusions (Ni) embedded into polyvinylidene fluoride matrix was prepared by using a simple blending and hot-molding technique. Effective medium approximations and percolation theory were employed in order to design and describe the dielectric behavior of such three-phase composites. Our experimental results showed that the static dielectric constant of such a three-phase composite can reach above 800 when the Ni concentration is close to its percolation threshold. Such composites have a potential to become capacitors and can be easily fabricated into various shapes due to its flexibility.

Ferroelectric Properties of Individual Barium Titanate Nanowires Investigated by Scanned Probe Microscopy

Abstract: We report scanned probe investigations on the ferroelectric properties of individual single-crystalline barium titanate nanowires. We show that nonvolatile electric polarization can be reproducibly induced and manipulated on these nanowires, thereby demonstrating that nanowires as small as 10 nm in diameter retain ferroelectricity. The coercive field for polarization reversal is determined to be ∼7 kV/cm, and the retention time for the induced polarization exceeds 5 days. These nanowires should provide promising materials for fundamental investigations on nanoscale ferroelectricity, and they may also be useful in nanoscale nonvolatile memory applications.

Large remanent polarization of (Bi, Nd)4Ti3O12 epitaxial thin films grown by metalorganic chemical vapor deposition

Abstract: (104)-oriented Bi4Ti3O12, La-substituted Bi4Ti3O12[(Bi3.44La0.56)Ti3O12] and Nd-substituted Bi4Ti3O12[(Bi3.54Nd0.46)Ti3O12] films were epitaxially grown on (111)SrRuO3//(111)SrTiO3 substrates at 700 °C by metalorganic chemical vapor deposition. All deposited films showed strong (104) orientations. The values of the remanent polarization (Pr) and coercive field (Ec) of the (104)-oriented epitaxial (Bi3.54Nd0.46)Ti3O12 thin film were 25 μC/cm2 and 135 kV/cm, respectively. This Pr value was larger than that of the (104)-oriented (Bi3.44La0.56)Ti3O12 film: Pr and Ec values of the (Bi3.44La0.56)Ti3O12 were 17 μC/cm2 and 145 kV/cm, respectively. These good ferroelectric properties of (Bi3.54Nd0.46)Ti3O12 films can be explained by a large tilting of TiO6 octahedra induced by the substitution of Nd3+, the ionic radius of which is smaller than that of La3+. Moreover, this Pr value is almost equal to that of commercially used lead zirconate titanate (PZT) films for nonvolatile ferroelectric random access memory (Fe...

Crystal structure and spiral magnetic ordering of BiFeO 3 doped with manganese

Abstract: Neutron powder diffraction has been performed on polycrystalline BiMnxFe1-xO3 (x=0, 0.1 and 0.2). The structures of the doped compounds are described by the space group R3c of ferroelectric BiFeO3. Refined structure parameters are presented. Mn doping generates microstructural changes manifested by broadening in the diffraction patterns. The lattice parameters show a non-linear behaviour from 4 K to 630 K. Mn doping results in a transformation of the long-range spiral spin modulation of BiFeO3 to a collinear antiferromagnetic structure with spins along c. The average magnetic moments and the ordering temperatures decrease with increasing Mn concentration.

Fully coupled, multi-axial, symmetric constitutive laws for polycrystalline ferroelectric ceramics

Abstract: In this paper, a general form for multi-axial constitutive laws for ferroelectric ceramics is constructed. The foundation of the theory is an assumed form for the Helmholtz free energy of the material. Switching surfaces and associated flow rules are postulated in a modified stress and electric field space such that a positive dissipation rate during switching is guaranteed. The resulting tangent moduli relating increments of stress and electric field to increments of strain and electric displacement are symmetric since changes in the linear elastic, dielectric and piezoelectric properties of the material are included in the switching surface. Finally, parameters of the model are determined for two uncoupled cases, namely non-remanent straining ferroelectrics and purely ferroelastic switching, and then for the fully coupled ferroelectric case.

Theory of polarization enhancement in epitaxial BaTiO$_3$/SrTiO$_3$ superlattices

Abstract: The spontaneous polarization of epitaxial BaTiO$_3$/SrTiO$_3$ superlattices is studied as a function of composition using first-principles density functional theory within the local density approximation. With the in-plane lattice parameter fixed to that of bulk SrTiO$_3$, the computed superlattice polarization is enhanced above that of bulk BaTiO$_3$ for superlattices with BaTiO$_3$ fraction larger than 40%. In contrast to their bulk paraelectric character, the SrTiO$_3$ layers are found to be {\it tetragonal and polar}, possessing nearly the same polarization as the BaTiO$_3$ layers. General electrostatic arguments elucidate the origin of the polarization in the SrTiO$_3$ layers, with important implications for other ferroelectric nanostructures.

Phase diagrams and dielectric response of epitaxial barium strontium titanate films: A theoretical analysis

Abstract: We develop phase diagrams for single-domain epitaxial barium strontium titanate films on cubic substrates as a function of the misfit strain based on a Landau–Devonshire phenomenological model similar to the one developed by Pertsev et al. [Phys. Rev. Lett. 80, 1988 (1998)]. The biaxial epitaxy-induced internal stresses enable phase transformations to unusual ferroelectric phases that are not possible in single crystals and bulk ceramics. The dielectric response of the films is calculated as a function of the misfit strain by taking into account the formation of misfit dislocations that relieve epitaxial stresses during deposition. It is shown that by adjusting the misfit strain via substrate selection and film thickness, a high dielectric response can be obtained, especially in the vicinity of structural instabilities. Theoretical estimation of the dielectric constant of (001) Ba0.7Sr0.3TiO3 and Ba0.6Sr0.4TiO3 films on (001) Si, MgO, LaAlO3, and SrTiO3 substrates as a function of misfit strain and film thickness is provided. An order-of-magnitude increase in the dielectric constant with increasing film thickness is expected for films on LaAlO3 and SrTiO3 substrates. A structural instability around 40 nm is predicted in films on MgO substrates accompanied by a substantial increase in the dielectric constant. For films on MgO substrates thicker than 40 nm, the analysis shows that the dielectric constant decreases significantly. We show that the theoretical approach not only predicts general trends but is also in good quantitative agreement with the experimental data reported in literature.

Maxwell-Wagner polarization in ceramic composites BaTiO3-(Ni0.3Zn0.7)Fe2.1O4

Abstract: Dense ceramic composites consisting of two phases, ferroelectric BaTiO3 and ferrite (Ni0.3Zn0.7)Fe2.1O4, were synthesized via the solid state reaction route. The results indicate that insulating BaTiO3 can be well compatible to the conductive phase (Ni0.3Zn0.7)Fe2.1O4. The electrical conduction and dielectric behavior of the materials vary with the ratio of the two phases. The dielectric behavior is greatly influenced by the conductive phase. At x=0.3, a very high apparent dielectric constant peak with frequency dispersion was observed, and attributed to Maxwell–Wagner polarization. The application of the Maxwell–Wagner polarization model in dielectric materials is briefly discussed.

Ferroelectric-relaxor behavior of Ba(Ti0.7Zr0.3)O3 ceramics

Abstract: Ferroelectric-relaxor behavior of Ba(Ti0.7Zr0.3)O3 ceramics is studied in the temperature range from 150 to 450 K. A broad dielectric peak with a high-dielectric maximum exhibits frequency dispersion. The dielectric relaxation rate follows the Vogel–Fulcher relation with E=0.21 eV and TVF=199.6 K. The polarization hysteresis loops were observed with a remnant polarization of 10 μC/cm2 at 175 K. The high-dielectric constant and high-polarization properties are expected to find practical applications at low temperatures.

Atomic Polarization and Local Reactivity on Ferroelectric Surfaces: A New Route toward Complex Nanostructures

Abstract: Atomic polarization in ferroelectric compounds is manipulated to control local electronic structure and influence chemical reactivity. Ferroelectric domains are patterned with electron beams or with probe tips, and electron exchange reactions occur preferentially on positive or negative domains. Using photo reduction from aqueous solution, metal nanoparticles are produced in predefined locations on an oxide substrate. Subsequently, organic molecules are reacted selectively to the particles. The process can be repeated to develop complex structures consisting of nanosized elements of semiconductors, metals, or functional organic molecules.

Effect of electrical boundary conditions on ferroelectric domain structures in thin films

Abstract: The domain structures in a ferroelectric thin film are studied using a phase-field model. A cubic-to-tetragonal ferroelectric phase transition in lead titanate thin film is considered. Both elastic interactions and electrostatic interactions are taken into account. The focus is on the effect of electrical boundary conditions on the domain morphologies and volume fractions. It is shown that different electric boundary conditions may have a significant effect on the domain structures.

Theory of low-frequency magnetoelectric effects in ferromagnetic-ferroelectric layered composites

Abstract: A theoretical model is presented for low-frequency magnetoelectric (ME) effects in bilayers of magnetostrictive and piezoelectric phases. An approach is proposed for the consideration of actual boundary conditions at the interface. An averaging method is used to estimate effective material parameters. The model predicts the strongest ME effect in cobalt ferrite-lead zirconate titanate (PZT) among ferrite based composites. The ME voltage coefficient for transverse field orientation is estimated to be 25–50% higher than for the longitudinal case. Comparison with data for multilayer samples reveals poor interface coupling in cobalt ferrite-PZT and ideal coupling in nickel ferrite-PZT.

Studies on ferroelectric perovskites and Bi‐layered compounds using micro‐Raman spectroscopy

Abstract: This paper provides a review of a systematic micro-Raman scattering study on various lead- and barium-based ABO3 perovskites (A = Pb, La, Ba, Sr, Ce, Gd, Nd and B = Ti, Zr), Aurivillius-type Bi-layered compounds (SrBi2Ta2O9, Bi4Ti3O12) and their solid solutions useful in a broad range of device applications. Various factors that influence the material properties such as particle size, stresses, stoichiometry, compositional homogeneity and their effects on phase transition were investigated. The processing conditions, A- and B-site substitution, size-dependent Raman spectra and the structure–property correlations are discussed in the bulk, thin film and nano-crystalline forms of these materials. A film thickness dependence stress study on lead titanate (PT) and lead zirconate titanate (PZT) films indicated that the nature of stress depends strongly on the lattice parameters of the film and substrate. The size effect was found to decrease the ferroelectric transition temperature in lead-based perovskite materials. Both ionic charge and radii induced changes in the Raman spectra of A- and B-site substituted perovskites and layered compounds were studied. A-site substitution in strontium bismuth tantalite (SBT) was found to induce a relatively linear variation of transition temperature compared with the B-site substituted SBT. Raman spectra of layered compounds and their solid solutions exhibited a strong dependence on dopants resulting in structural modifications. Copyright © 2002 John Wiley & Sons, Ltd.

The interface screening model as origin of imprint in PbZrxTi1−xO3 thin films. I. Dopant, illumination, and bias dependence

Abstract: Comprehensive imprint measurements on PbZrxTi1−xO3 (PZT) thin films were carried out. Different models, which were proposed in literature to explain imprint in ferroelectric thin films or a similar aging effect (internal bias) in ferroelectric bulk material, are reviewed. Discrepancies between the experimental results obtained on the PZT films in this work and the prediction of the literature models indicate that these models do not describe the dominant imprint mechanism in PZT thin films. Hence, in this work a model is proposed which suggests imprint to be caused by a strong electric field within a thin surface layer in which the ferroelectric polarization is smaller or even absent compared to the bulk of the film. With the proposed imprint model the influence of important experimental parameters like dopant, illumination, and bias dependence can be qualitatively explained.

Temperature and thickness dependent permittivity of (Ba,Sr)TiO3 thin films

Abstract: The temperature and thickness dependence of permittivity of (Ba,Sr)TiO3 has been investigated. The films were deposited by liquid-source metalorganic chemical vapor deposition onto Pt/SiO2/Si, with thicknesses ranging from 15 to 580 nm. The dielectric response was measured from 100 to 520 K. As film thickness decreased, the maximum dielectric constant decreased, the temperature at which the maximum dielectric constant occurred decreased, and the peak in the dielectric constant became more diffuse. A model incorporating a thickness independent interior and a nonferroelectric surface cannot account for these thickness dependencies. To appropriately model these observations a physical model containing thickness and temperature dependent interior and surface components is necessary.

Tbit/inch2 ferroelectric data storage based on scanning nonlinear dielectric microscopy

Abstract: Nanosized inverted domain dots in ferroelectric materials have potential applications in ultrahigh-density rewritable data storage systems. Here, a data storage system based on scanning nonlinear dielectric microscopy and thin films of ferroelectric single-crystal lithium tantalite is presented. Through domain engineering, nanosized inverted domain dots have been successfully formed at a data density of 1.50 Tbit/in.2.

Impact of thermal strain on the dielectric constant of sputtered barium strontium titanate thin films

Abstract: Barium strontium titanate thin films were deposited by sputtering on Pt/SiO2 structures using five different host substrates: magnesium oxide, strontium titanate, sapphire, silicon, and vycor glass. These substrates were chosen to provide a systematic change in thermal strain while maintaining the same film microstructure. All films have a weakly textured microstructure. Temperature dependent dielectric measurements from 100–500 K determined that decreasing thermal expansion coefficient of the host substrate (i.e., larger tensile thermal strain) reduced the film dielectric permittivity. The experimentally determined Curie–Weiss temperature decreased with increasing tensile thermal strain and the Curie–Weiss constant increased with tensile strain as predicted by Pertsev et al. [J. Appl. Phys. 85, 1698 (1999)].