Study of relaxor behavior of 0.7Pb(Mg1/3Nb2/3)O-3-0.3PbTiO(3) thin films

Relaxor properties of polycrystalline 0.7Pb(Mg1/3Nb2/3)O-3-0.3PbTiO(3) (PMN-PT) thin films were studied in terms of the diffuse nature of phase transition along with the frequency dispersion of temperature (T-m) at which the dielectric constant exhibits maximum value. Existence of remnant polarization (P-r) above the phase transition temperature, which is a characteristic property of typical relaxor ferroelectric has also been observed in the present case. The films exhibited a gradual decrease of remnant polarization with increase of temperature. Among the different models of relaxor ferroelectric, Vogel-Fulcher model has been found to be suitable to describe the frequency dispersion of T-m in this case. Freezing of dipole moment with decrease of temperature was thought to be the origin of the temperature dependence of dielectric dispersion.

Effect of neodymium (Nd) doping on the dielectric and ferroelectric characteristics of sol-gel derived lead zirconate titanate (53/47) thin films

The results of the studies on the effect of rare earth Nd doping on the phase formation behavior and electrical properties of sol-gel derived Pb-1.05(Zr0.53Ti0.47)O-3 (PZT) thin films are presented. The perovskite phase is obtained up to 5 at. % doping and beyond that pyrochlore phase was found to coexist with the perovskite phase in all the films. The transition temperature of undoped lead zirconate titanate (PZT) film was found to be reduced with Nd doping. The Nd doped films also exhibited typical relaxor-type behavior and a diffuse phase transition, similar to that observed in relaxor materials. The introduction of Nd into the PZT lattice probably introduces disorder in the B site of ABO(3) lattice, which causes the observed dielectric relaxation. Efforts were made to isolate the irreversible component contributions in low field dielectric and high field polarization switching behavior. (C) 2001 American Institute of Physics.

Transmission electron microscopy study of domain structures in ferroelectric SrBi2Nb2O9 ceramics

A transmission electron microscopy study has been carried out on the domain structures of SrBi2Nb2O9 (SBN) ferroelectric ceramics which belong to the Aurivillius family of bismuth layered perovskite oxides. SBN is a potential candidate for Ferroelectric Random access memory (FeRAM) applications. The 90° ferroelectric domains and antiphase boundaries (APBs) were identified with dark field imaging techniques using different superlattice reflections which arise as a consequence of octahedral rotations and cationic shifts. The 90° domain walls are irregular in shape without any faceting. The antiphase boundaries are less dense compared to that of SrBi2Ta2O9(SBT). The electron microscopy observations are correlated with the polarization fatigue nature of the ceramic where the domain structures possibly play a key role in the fatigue- free behavior of the Aurivillius family of ferroelectric oxides.

Antiferroelectriclike polarization behavior in compositionally varying (1-x) Pb(Mg1/3Nb2/3)O3–(x) PbTiO3 multilayers

Compositionally varying multilayers of (1−x) Pb(Mg1/3N2/3)O3–(x) PbTiO3 were fabricated using pulsed laser ablation technique. An antiferroelectriclike polarization hysteresis was observed in these relaxor based multilayer systems. The competition among the intrinsic ferroelectric coupling in the relaxor ferroelectrics and the antiferroelectric coupling among the dipoles at the interface gives rise to an antiferroelectriclike polarization behavior. An increment in the coercive field and the applied field corresponding to the polarization flipping at low temperatures, provide further insight on the competition among the long-range ferroelectric interaction and the interfacial interaction in the polarization behavior of these relaxor multilayers.

Growth and ferroelectric properties of Bi2VO5.5 thin films with metallic LaNiO3 electrodes

Novel ferroelectric bismuth vanadate, Bi2VO5.5 (BVO), thin films have been grown between lattice matched metallic LaNiO3 (LNO) layers deposited on SrTiO3 (STO) by the pulsed laser deposition technique. LNO/BVO/LNO/STO and Au/BVO/LNO/STO trilayer structures exhibited c‐oriented (001) growth of BVO. LNO has been found to be a good metallic electrode with sheet resistance ∼20 Ω in addition to aiding c‐axis oriented BVO growth. The dielectric constant, ϵr of LNO/BVO/LNO/STO, at 300 K was about 12. However, when an Au electrode was used on top of BVO/LNO/STO film, it showed a significant improvement in the dielectric constant (ϵr=123). The ferroelectric properties of BVO thin films have been confirmed by hysteresis behavior with a remnant polarization, Pr=4.6×10−8 C/cm2 and coercive field, Ec=23 kV/cm at 300 K.

Improved ferroelectric and leakage properties in symmetric BiFeO3/SrTiO3 superlattice

Symmetric BiFeO3/SrTiO3 superlattices were fabricated by pulsed laser deposition on SrTiO3 (100) substrates. Frequency independent and near saturated P-E hysteresis was observed in the case of a superlattice (periodicity of ∼ 11 nm) as compared to leaky hysteresis observed in epitaxial BiFeO3. Room temperature leakage current density of the superlattice was almost two orders of magnitude lower than that of BiFeO3. Observed leakage current behavior in case of both BiFeO3 and superlattice indicates the dominance of space charge limited conduction. Improvement in ferroelectric property was discussed in connection to enhanced epitaxial strain, reduced leakage current, and electrostatic interaction between BiFeO3 and SrTiO3.

Ferroelectric interaction and polarization studies in BaTiO3/SrTiO3 superlattice

Ferroelectric superlattice structures consisting of alternating layers of BaTiO3 and SrTiO3 with variable interlayer thickness were grown on Pt (111)/TiO2/SiO2/Si (100) substrates by pulsed laser deposition. The presence of superlattice reflections in the x-ray diffraction pattern clearly showed the superlattice behavior of the fabricated structures over a range of 6.4–20 nm individual layer thicknesses. Depth profile conducted by secondary ion mass spectrometry analysis showed a periodic concentration of Ba and Sr throughout the film. Polarization hysteresis and the capacitance-voltage characteristics of these films show clear size dependent ferroelectric characteristics. The spontaneous (Ps) and remnant (Pr) polarizations increase gradually with decreasing periodicity, reach a maximum at a finite thickness and then decrease. The competition between the size effect and long-range ferroelectric interaction is suggested as a possible reason for this phenomenon. The temperature dependence of Ps and Pr shows a single ferroelectric phase transition, and the Curie temperature is estimated to be about 316 K. The curve shows that the ferroelectric superlattice tends to form an artificial material, responding as a single structure with an averaged behavior of both the parent systems.

Metastable monoclinic and orthorhombic phases and electric field induced irreversible phase transformation at room temperature in the lead-free classical ferroelectric BaTiO3

For decades it has been a well-known fact that among the few ferroelectric compounds in the perovskite family, namely, BaTiO3, KNbO3, PbTiO3, and Na1/2Bi1/2TiO3, the dielectric and piezoelectric properties of BaTiO3 are considerably higher than the others in polycrystalline form at room temperature. Further, similar to ferroelectric alloys exhibiting morphotropic phase boundary, single crystals of BaTiO3 exhibit anomalously large piezoelectric response when poled away from the direction of spontaneous polarization at room temperature. These anomalous features in BaTiO3 remained unexplained so far from the structural standpoint. In this work, we have used high-resolution synchrotron x-ray powder diffraction, atomic resolution aberration-corrected transmission electron microscopy, in conjunction with a powder poling technique, to reveal that at 300 K (i) the equilibrium state of BaTiO3 is characterized by coexistence of metastable monoclinic Pm and orthorhombic (Amm2) phases along with the tetragonal phase, and (ii) strong electric field switches the polarization direction from the 001] direction towards the 101] direction. These results suggest that BaTiO3 at room temperature is within an instability regime, and that this instability is the fundamental factor responsible for the anomalous dielectric and piezoelectric properties of BaTiO3 as compared to the other homologous ferroelectric perovskite compounds at room temperature. Pure BaTiO3 at room temperature is therefore more akin to lead-based ferroelectric alloys close to the morphotropic phase boundary where polarization rotation and field induced ferroelectric-ferroelectric phase transformations play a fundamental role in influencing the dielectric and piezoelectric behavior.

Tuning of dielectric, pyroelectric and ferroelectric properties of 0.715Bi(0.5)Na(0.5)TiO(3)-0.065BaTiO(3)-0.22SrTiO(3) ceramic by internal clamping

This study systematically investigates the phenomenon of internal clamping in ferroelectric materials through the formation of glass-ceramic composites. Lead-free 0.715Bi(0.5)Na(0.5)TiO(3)-0.065BaTiO(3)-0.22SrTiO(3) (BNT-BT-ST) bulk ferroelectric ceramic was selected for the course of investigation. 3BaO - 3TiO(2) - B2O3 (BTBO) glass was then incorporated systematically to create sintered samples containing 0%, 2%, 4% and 6% glass (by weight). Upon glass induction features like remnant polarization, saturation polarization, hysteresis losses and coercive field could be varied as a function of glass content. Such effects were observed to benefit derived applications like enhanced energy storage density similar to 174 k J/m(3) to similar to 203 k J/m(3) and pyroelectric coefficient 5.7x10(-4) Cm-2K-1 to 6.8x10(-4) Cm-2K-1 by incorporation of 4% glass. Additionally, BNT-BT-ST depolarization temperature decreased from 457K to 431K by addition of 4% glass content. Glass incorporation could systematically increases diffuse phase transition and relaxor behavior temperature range from 70 K to 81K and 20K to 34 K, respectively when 6% and 4% glass content is added which indicates addition of glass provides better temperature stability. The most promising feature was observed to be that of dielectric response tuning. It can be also used to control (to an extent) the dielectric behavior of the host ceramic. Dielectric permittivity and losses decreased from 1278 to 705 and 0.109 to 0.107 for 6% glass, at room temperature. However this reduction in dielectric constant and loss increases pyroelectric figures of merit (FOMs) for high voltage responsivity (F-v) high detectivity (F-d) and energy harvesting (F-e) from 0.018 to 0.037 m(2)C(-1), 5.89 to 8.85 mu Pa-1/2 and 28.71 to 61.55 Jm(-3)K(-2), respectively for 4% added ceramic-glass at room temperature. Such findings can have huge implications in the field of tailoring ferroelectric response for application specific requirements. (C) 2015 Author(s).

Ferrocene in conjugation with a Fischer carbene: Synthesis, NLO, and electrochemical behavior of a novel organometallic push-pull system

Using an iterative sequence of Wittig olefination, reduction, oxidation, and condensation of an active methylene group to carbonyl, it was possible to prepare a series of organometallic push-pull molecules [(CO)(5)M=C(OCH3)(-CH=CH-)(n)(C5H4)Fe(C5H5), M = W, Cr, n = 1-4] in which ferrocene is the donor element and a Fisher carbene moeity is the acceptor group. The molecular first hyperpolarizability beta was determined by hyper-Rayleigh scattering experiments. The beta values ranged from 110 x 10(-30) to 2420 x 10(-30) esu in acetonitrile, and they are among the highest reported for organometallic molecules so far. Electrochemical measurements are consistent with the push-pull nature of these compounds.

Crossover from Ising to mean-field critical behavior in an aqueous electrolyte solution

The near-critical behavior of the susceptibility deduced from light-scattering measurements in a ternary liquid mixture of 3-methylpyridine, water, and sodium bromide has been determined. The measurements have been performed in the one-phase region near the lower consolute points of samples with different concentrations of sodium bromide. A crossover from Ising asymptotic behavior to mean-field behavior has been observed. As the concentration of sodium bromide increases, the crossover becomes more pronounced, and the crossover temperature shifts closer to the critical temperature. The data are well described by a model that contains two independent crossover parameters. The crossover of the susceptibility critical exponent γ from its Ising value γ=1.24 to the mean-field value γ=1 is sharp and nonmonotonic. We conclude that there exists an additional length scale in the system due to the presence of the electrolyte which competes with the correlation length of the concentration fluctuations. An analogy with crossover phenomena in polymer solutions and a possible connection with multicritical phenomena is discussed.

Effect of antimony addition on the thermal and electrical-switching behavior of bulk Se-Te glasses

The thermal properties and electrical-switching behavior of semiconducting chalcogenide SbxSe55-xTe45 (2 <= x <= 9) glasses have been investigated by alternating differential scanning calorimetry and electrical-switching experiments, respectively. The addition of Sb is found to enhance the glass forming tendency and stability as revealed by the decrease in non-reversing enthalpy Delta H-nr. and an increase in the glass-transition width Delta T-g. Further, the glass-transition temperature of SbxSe55-xTe45 glasses, which is a measure of network connectivity, exhibits a subtle increase, suggesting a meager network growth with the addition of Sb. The crystallization temperature is also observed to increase with Sb content. The SbxSe55-xTe45 glasses (2 <= x <= 9) are found to exhibit memory type of electrical switching, which can be attributed to the polymeric nature of network and high devitrifying ability. The metallicity factor has been found to dominate over the network connectivity and rigidity in the compositional dependence of switching voltage. which shows a profound decrease with the addition of Sb.

Colossal dielectric behavior of semiconducting Sr2TiMnO6 ceramics

Manganitelike double perovskite Sr2TiMnO6 (STMO) ceramics fabricated from the powders synthesized via the solid-state reaction route, exhibited dielectric constants as high as similar to 10(5) in the low frequency range (100 Hz-10 kHz) at room temperature. The Maxwell-Wagner type of relaxation mechanism was found to be more appropriate to rationalize such high dielectric constant values akin to that observed in materials such as KxTiyNi(1-x-y)O and CaCu3Ti4O12. The dielectric measurements carried out on the samples with different thicknesses and electrode materials reflected the influence of extrinsic effects. The impedance studies (100 Hz-10 MHz) in the 180-300 K temperature range revealed the presence of two dielectric relaxations corresponding to the grain boundary and the electrode. The dielectric response of the grain boundary was found to be weakly dependent on the dc bias field (up to 11 V/cm). However, owing to the electrode polarization, the applied ac/dc field had significant effect on the low frequency dielectric response. At low temperatures (100-180 K), the dc conductivity of STMO followed a variable range hopping behavior. Above 180 K, it followed the Arrhenius behavior because of the thermally activated conduction process. The bulk conductivity relaxation owing to the localized hopping of charge carriers obeyed the typical universal dielectric response.

Flow behavior of long chain plasticizing liquids: Segment size calculations in carboxylate esters

This is the first comprehensive report on the calculation of segment size, which signifies the asic unit of flow in long chain plasticizing liquids, by a novel multi-pronged approach. Unlike,low molecular weight liquids and high polymer melts these complex long chain liquids encompasses the least understood domain of the liquid state. In the present work the flow behaviour of carboxylate ester (300-900 Da) has been explained through segmental motion taking into account the independence of molecular weight region. The segment size have been calculated by various methods based on satistical thermodynamics, molecular dynamics and group additivity nd their merits analysed.

Colossal dielectric behavior of semiconducting $Sr_{2}TiMnO_{6}$ ceramics

Manganitelike double perovskite Sr2TiMnO6 (STMO) ceramics fabricated from the powders synthesized via the solid-state reaction route, exhibited dielectric constants as high as similar to 10(5) in the low frequency range (100 Hz-10 kHz) at room temperature. The Maxwell-Wagner type of relaxation mechanism was found to be more appropriate to rationalize such high dielectric constant values akin to that observed in materials such as KxTiyNi(1-x-y)O and CaCu3Ti4O12. The dielectric measurements carried out on the samples with different thicknesses and electrode materials reflected the influence of extrinsic effects. The impedance studies (100 Hz-10 MHz) in the 180-300 K temperature range revealed the presence of two dielectric relaxations corresponding to the grain boundary and the electrode. The dielectric response of the grain boundary was found to be weakly dependent on the dc bias field (up to 11 V/cm). However, owing to the electrode polarization, the applied ac/dc field had significant effect on the low frequency dielectric response. At low temperatures (100-180 K), the dc conductivity of STMO followed a variable range hopping behavior. Above 180 K, it followed the Arrhenius behavior because of the thermally activated conduction process. The bulk conductivity relaxation owing to the localized hopping of charge carriers obeyed the typical universal dielectric response.