High-frequency dielectric spectroscopy of batio3 core - silica shell nanocomposites: Problem of interdiffusion

Three types of BaTiO3 core - amorphous nano-shell composite ceramics were processed from the same core-shell powder by standard sintering, spark-plasma sintering and two-step sintering techniques and characterized by XRD, HRSEM and broad-band dielectric spectroscopy in the frequency range 10^3 - 10^13 Hz including the THz and IR range. The samples differed by porosity and by the amount of interdiffusion from the cores to shells, in correlation with their increasing porosity. The dielectric spectra were also calculated using suitable models based on effective medium approximation. The measurements revealed a strong dielectric dispersion below the THz range, which cannot be explained by the modeling, and whose strength was in correlation with the degree of interdiffusion. We assigned it to an effect of the interdiffusion layers, giving rise to a strong interfacial polarization. It appears that the high-frequency dielectric spectroscopy is an extremely sensitive tool for detection of any gradient layers and sample inhomogeneities even in dielectric materials with negligible conductivity

Infrared and THz studies of polar phonons and improper magnetodielectric effect in multiferroic BFO3 ceramics

BFO3 ceramics were investigated by means of infrared reflectivity and time domain THz transmission spectroscopy at temperatures 20 - 950 K, and the magnetodielectric effect was studied at 10 - 300 K, with the magnetic field up to 9 T. Below 175 K, the sum of polar phonon contributions into the permittivity corresponds to the value of measured permittivity below 1 MHz. At higher temperatures, a giant low-frequency permittivity was observed, obviously due to the enhanced conductivity and possible Maxwell-Wagner contribution. Above 200 K the observed magnetodielectric effect is caused essentially through the combination of magnetoresistance and the Maxwell-Wagner effect, as recently predicted by Catalan (Appl. Phys. Lett. 88, 102902 (2006)). Since the magnetodielectric effect does not occur due to a coupling of polarization and magnetization as expected in magnetoferroelectrics, we call it improper magnetodielectric effect. Below 175 K the magnetodielectric effect is by several orders of magnitude lower due to the decreased conductivity. Several phonons exhibit gradual softening with increasing temperature, which explains the previously observed high-frequency permittivity increase on heating. The observed non-complete phonon softening seems to be the consequence of the first-order nature of the ferroelectric transition.Comment: subm. to PRB. revised version according to referees' report

Magnetodielectric effect and optic soft mode behaviour in quantum paraelectric EuTiO3 ceramics

Infrared reflectivity and time-domain terahertz transmission spectra of EuTiO3 ceramics revealed a polar optic phonon at 6 - 300K, whose softening is fully responsible for the recently observed quantum paraelectric behaviour. Even if our EuTiO3 ceramics show lower permittivity than the single crystal due to a reduced density and/or small amount of secondary pyrochlore Eu2Ti2O7 phase, we confirmed the magnetic field dependence of the permittivity, also slightly smaller than in single crystal. Attempt to reveal the soft phonon dependence at 1.8K on the magnetic field up to 13T remained below the accuracy of our infrared reflectivity experiment

Polar lattice vibrations and phase transition dynamics in Pb(Zr1-xTix)O-3

Infrared (IR) reflectivity spectra of nominally pure Pb(Zr1-xTix)O-3 ceramics with different Ti/Zr concentration (x = 0.42-0.58) were measured and evaluated, along with the time-domain terahertz transmittance spectra in the temperature range 10 K-900 K. The temperature dependence of the low-frequency vibrations, related to Pb atoms, was analyzed in terms of two overdamped modes-a soft mode and an anharmonic hopping central mode-in the cubic and high-temperature ferroelectric phase and three main vibrations in the low-temperature ferroelectric phase with the doubled unit cell: two E-symmetry modes (the soft mode and a mode corresponding to antiphase vibrations of neighboring Pb atoms in the terahertz range) and the antiferrodistortive mode producing the antiphase tilts of the oxygen octahedra. The last bare mode is not IR active, but it becomes activated by coupling with the soft mode. As predicted by theory, the intrinsic permittivity of Pb(Zr1-xTix)O-3 has a maximum at the morphotropic phase boundary, although this represents just a small percentage of the total permittivity at lower frequencies. Its maximum is linked to the softening of the anharmonic vibrations of Pb ions, perpendicular to the polarization, and shifts from x = 0.48 at room temperature to x = 0.52 at 10 K