Analysis of polarization behavior in relaxation of BaTiO₃-based ferroelectrics using wideband dielectric spectroscopy

Wideband dielectric spectra from the kilohertz to terahertz range are discussed for BaTiO?-based ferroelectrics. Ceramics of BaTiO? (BT), Ba(0.6)Sr(0.4)TiO? (BST-0.6), and BaZr(0.25)Ti(0.75)O? (BZT-0.25) were selected as normal ferroelectrics, ferroelectrics with diffuse phase transition (DPT ferroelectrics), and relaxor ferroelectrics, respectively. The variation of ionic polarization in both BT and BST-0.6 ceramics with temperature could be explained by the softening of the soft phonon mode. In BZT-0.25, a permittivity anomaly at the dielectric maximum temperature (T(m)) at low frequencies is not attributed to the softening of the soft phonon mode, but originates from the permittivity derived from the dipole polarization (?(dipole)). Relaxor behavior in BZT-0.25 is derived from the increase in the depression of ?(dipole) on cooling across the T(m) with increasing frequency. In dipole polarization, BT, BST- 0.6, and BZT-0.25 all exhibited a similar tendency of ?(dipole) above the Curie temperature (T(c)) and T(m). However, behavior of ?(dipole) below the T(c) can be explained by the ferroelectric domains in BT, whereas the variation of ?(dipole) below the Tm could be explained by growth process of polar nanoregions (PNRs) in BST-0.6 and BZT-0.25. Regarding this, BT can be distinguished from BST-0.6 and BZT-0.25. Relaxation in BT could be interpreted as successive change in polarization mechanism from normal ferroelectrics to relaxor ferroelectrics via DPT ferroelectrics.     

Mechanism of capacitance aging under DC-bias field in X7R-MLCCs

Capacitance aging under DC electric fields has been studied on multilayer ceramic capacitors (MLCCs) with the X7R characteristics. The capacitance change with time was divided into two stages, the first- and the second-stage. The first-stage was due to the nonlinear permittivity of dielectrics and it should not be involved in the aging phenomenon. The second-stage depended on the MnO content, grain size and firing condition of dielectrics. From the behavior of the second-stage, it was concluded that the capacitance aging was caused by the 90-degree domain switching in BaTiO₃ in the core. The first-stage was due to the nonlinear permittivity but the domain switching was also included in the first-stage if the domain walls moved by the first application of DC field. The change in the aging behavior with the intensity of DC field could be explained by separating capacitance change into the nonlinear permittivity and the domain switching according to the mechanism proposed in this study.     

Enhancement of Q(m) by co-doping of Li and Cu to potassium sodium niobate lead-free ceramics.

Lead-free piezoelectric ceramics KNN modified by Li-substitution and CuO addition have been synthesized, and the piezoelectric and dielectric properties were measured. A morphotropic phase boundary (MPB) between orthorhombic and tetragonal phases was formed with Li-substitution. The co doping of Li and Cu markedly enhanced the mechanical quality factor (Q(m)) in comparison with the sole doping of Li and Cu. Anomalous anti ferroelectric-like hysteresis curves were observed in 2 mol% CuO-doped ceramics. The anti-ferroelectric-like curves were changed to that of normal ferroelectrics following poling. A model based on the formation of the internal bias field (Ei) due to the movements of space charges was proposed to explain these phenomena. It was considered that the Ei stabilized the spontaneous polarization (Ps) and suppressed the domain wall motion to enhance the Q(m). The highest Qm obtained in this study was 742. The [(Na0(0.5)K0(0.5))(0.96)Li0(0.04) ] NbO(3) + 0.45 mol% CuO ceramics showed a high Q(m) value of 414 with a high piezoelectric constant d(33) of 100 pC/N.     

Enhancement of Q/sub m/by Co-Doping of Li and Cu to Potassium Sodium Niobate Lead-Free Ceramics

Lead-free piezoelectric ceramics KNN modified by Li-substitution and CuO addition have been synthesized, and the piezoelectric and dielectric properties were measured. A morphotropic phase boundary (MPB) between orthorhombic and tetragonal phases was formed with Li-substitution. The co-doping of Li and Cu markedly enhanced the mechanical quality factor (Q_m) in comparison with the sole doping of Li and Cu. Anomalous anti-ferroelectric-like hysteresis curves were observed in 2 mol% CuO-doped ceramics. The anti-ferroelectric-like curves were changed to that of normal ferroelectrics following poling. A model based on the formation of the internal bias field (Ei) due to the movements of space charges was proposed to explain these phenomena. It was considered that the Ei stabilized the spontaneous polarization (Pa) and suppressed the domain wall motion to enhance the Q_m. The highest Q_m obtained in this study was 742. The [(Na_0.5K_0.5)_0.96Li_0.04] NbO₃ + 0.45 mol% CuO ceramics showed a high Q_m value of 414 with a high piezoelectric constant d₃₃ of 100 pC/N.     

Effects of gassericins A and T, bacteriocins produced by Lactobacillus gasseri, with glycine on custard cream preservation

Lactobacillus gasseri LA39 and LA158 isolated from human-infant feces produce bacteriocins named gassericins A and T, respectively. Both gassericins have high heat stability (121°C, 10 min), good pH tolerance (pH 2-11), and strong bactericidality against many gram-positive bacteria, especially lactic acid bacteria, and thus are expected to be effective food preservatives. A microwell plate assay against 12 strains of custard cream spoilage bacteria showed that the gassericins had broader antibacterial spectra than nisin A. Although the gassericins allowed gram-negative isolates to grow, they successfully inhibited the growth of all tested bacterial strains in microwells with the addition of glycine. Glycine was bacteriostatic against many strains except lactic acid bacteria. For practical use, gassericin A was efficiently produced by cultivation in a food-grade medium improved using cheese whey, nourishing proteose peptone, and surfactant yolk lecithin. The practical preservative effect of gassericin A and glycine was verified from the viability of 4 isolated strains, Bacillus cereus, Lactococcus lactis ssp. lactis, Achromobacter denitrificans, and Pseudomonas fluorescens, in custard creams. Custard cream containing 123 arbitrary units of gassericin A per milliliter entirely growth-inhibited the 2 gram-positive strains. In custard cream containing an insufficient amount of gassericin A (49 arbitrary units/mL), the gram-positive strains gradually grew but were completely inhibited by the addition of 0.5% (wt/wt) glycine. The 2 gram-negative strains did not multiply even in the additive-free custard cream, probably because of the unsuitable growth environment. This is the first report showing the combined effect of bacteriocin and glycine and their application for food preservation, which may be helpful for future use in the food industry.     

Anomalous dielectric and optical properties in perovskite-type artificial superlattices

Perovskite-type BaTiO₃/SrTiO₃ (BTO/STO) artificial superlattices were fabricated by molecular beam epitaxy process and their dielectric properties and refractive indices were measured. A large leakage current was observed in the films on Nb-doped STO substrate. Dielectric permittivity was therefore measured using planer interdigital electrodes. Fine planer electrodes were necessary to reduce the penetration of electric flux into the substrate. Interdigital electrodes were formed by electron-beam lithography. Dielectric permittivity of superlattices along the film surface was determined using electromagnetic field analysis. It was found that the dielectric permittivity of the BTO/STO superlattice with the period of 10 unit cells showed a maximum value above 30,000, which was almost independent from frequency up to 110 MHz. The refractive index of superlattices measured with a spectroscopic ellipsometer also showed the highest value when the period was 10 unit cells. This indicated that the structure of superlattices affected not only the ionic polarization but also the electric polarization. The origin of anomalous properties observed in superlattices may be interpreted by the strains induced into the film.     

Broadband spectroscopy of the complex conductivity of polycrystalline yttria-stabilized zirconia

Broadband conductivity spectra from 100 to 10¹⁴ Hz (100 THz) were acquired for yttria-stabilized zirconia (10 mol% Y₂O₃-doped ZrO₂, 10YSZ) to quantify contributions from conduction due to the electrolyte-electrode interface, grain boundaries, universal dielectric response (UDR), and optical phonons. The UDR contribution governed the intrinsic conductivity at all frequencies except specific frequencies in the terahertz range, where phonon contributions governed conductivity for both ceramics and single crystals. UDR parameters σ₀ and σ_dc increased with increasing temperature, resulting in increased microwave conductivity. The complex conductivity converged at frequencies of hundreds of gigahertz due to a decrease in the power-law constant, s, with increasing temperature. The optical phonon contribution to the total conductivity, due to an increase in the damping factor γ_1TO with increasing temperature, was small, while the phonon-mode frequency ω_1TO affected the microwave conductivity of 10YSZ.     

Effect of material constants on power output in piezoelectric vibration-based generators

A possible power output estimation based on material constants in piezoelectric vibration-based generators is proposed. A modified equivalent circuit model of the generator was built and was validated by the measurement results in the generator fabricated using potassium sodium niobate-based and lead zirconate titanate (PZT) ceramics. Subsequently, generators with the same structure using other PZT-based and bismuth-layered structure ferroelectrics ceramics were fabricated and tested. The power outputs of these generators were expressed as a linear functions of the term composed of electromechanical coupling coefficients k(sys)(2) and mechanical quality factors Q*(m) of the generator. The relationship between device constants (k(sys)(2) and Q*(m)) and material constants (k(31)(2) and Q(m)) was clarified. Estimation of the power output using material constants is demonstrated and the appropriate piezoelectric material for the generator is suggested.     

Dielectric properties of BaTiO3-based ceramics measured up to GHz region

A new measuring method and analyzing procedure were proposed to determine the complex dielectric constant of materials with relatively high dielectric constant by a lumped impedance measurement using impedance analyzer. Samples used for the measurement were (Ba_0.6Sr_0.4)TiO₃ (BST) and Ba(Zr_0.25Ti_0.75)O₃ (BZT) ceramics. Micro planar electrodes were formed on the surface of samples by electron beam lithography followed by lift-off method. Complex admittances of these samples were measured up to 3 GHz at different temperatures. Electromagnetic simulations were performed for determining the relative dielectric constant and dielectric loss. The complex dielectric constant vs frequency curves of Ba(Zr_0.25Ti_0.75)O₃ showed a broad dielectric relaxation, while that of (Ba_0.6Sr_0.4)TiO₃ was almost flat up to 3 GHz on high-temperature side of T _m at which dielectric constant shows maximum value. Dielectric dispersion properties were discussed from the viewpoint of diffuse phase transition in ferroelectrics.     

Preparation of barium titanate nanocube particles by solvothermal method and their characterization

Barium titanate (BaTiO₃) nanocube particles below 20 nm were prepared by solvothermal method. A selection of organic solvent and inorganic materials of Ba and Ti sources was most important for the preparation of nanocubes. A nucleation and particle growth of BaTiO₃ nanoparticles led to a formation of the BaTiO₃ nanocubes with a size of 10–15 nm at temperatures above 200 °C.