Enhanced ferroelectricity of CaBi2Nb2O9-based high-temperature piezoceramics by pseudo-tetragonal distortion

(LiBi)-doped CaBi₂Nb₂O₉ (CBN) ceramics were synthesized by the conventional solid-state sintering method. The effects of (LiBi) additives on the crystalline structure were explored by Rietveld refinements. The results showed that pseudo-tetragonal distortion was induced by (LiBi) additives when x ≥ 0.35. This structural distortion increased the spontaneous polarization along a-axis and decreased the quits spontaneous polarization along b-axis, which was beneficial to the polarization switching, thus promoting the ferroelectricity and decreasing the coercive field (E_C) of CBN based ceramics. The Ca_0.60(Li_0.5Bi_0.5)_0.40Bi₂Nb₂O₉ (CBNLB-40) ceramics possess the optimum ferroelectric property with 2P_r of 10 μC/cm² and a coercive field (E_C) lower than 100 kV/cm. Moreover, it exhibits a good ferroelectric fatigue-free property within 10⁷ switched cycles. This work may provide a new method to promote the performance of Aurivillius ferroelectric-based non-volatile memory devices.     

On Structure,Optical Properties and Photodegradated Ability of Aurivillius‐Type Bi3TiNbO9 Nanoparticles

Bi₃TiNbO₉ nanoparticles with an acceptor dopant of Ni²⁺ ion were prepared by the conventional Pechini sol–gel synthesis. The X‐ray polycrystalline diffraction measurements (XRD) and the Rietveld refinements of Bi₃TiNbO₉ samples were completed. The surface property of Bi₃TiNbO₉ nanoparticles was investigated by transmission electron microscope, scanning electron microscope), and N₂ adsorption–desorption isotherms. Bi₃TiNbO₉ nanoparticles showed an optical band gap with energy of 3.1 eV in the UV region. While the Ni²⁺‐doping could greatly reduce the band energy of Bi₃TiNbO₉:xNi²⁺ nanoparticles to 2.79 eV (x = 0.05) and 2.61 eV (x = 0.1). This indicates that the Ni‐doped samples could be excited by UV–visible light. The photocatalytic abilities were tested by the photodegradation on methylene blue solution (MB) and phenol solutions excited by visible light. Accordingly, the photocatalytic activity was improved by the Ni‐doping in B‐sites in this Aurivillius‐type structure. The results concluded that Bi₃TiNbO₉:Ni²⁺ would be a possible candidate as a visible light‐driven photocatalyst. The effective photocatalysis was discussed on the structure characteristic and experiment such as polarized Aurivillius (Bi₂O₂)²⁺ layers, luminescence, and decay lifetimes, etc.     

Impedance analysis of thermally modified SrBi2(Nb0.5Ta0.5)2O9 ceramics

Aurivillius SrBi₂(Nb_0.5Ta_0.5)₂O₉ (SBNT 50/50) ceramics were prepared using the conventional solid-state reaction method. The obtained samples were thermally modified in high vacuum to study the influence of the formed defects on the dielectric and electrical properties of the samples. Scanning electron microscopy with an energy dispersion X-ray spectrometer was applied to investigate the grain structure and stoichiometry of the studied ceramics. Their dielectric properties were determined by impedance spectroscopy measurements. A strong low frequency dielectric dispersion was found to exist in this material which was controlled by thermal modification of the tested ceramics. This phenomenon can be ascribed to the presence of ionized space charge carriers such as oxygen and bismuth vacancies. The dielectric relaxation was defined on the basis of an equivalent circuit. Moreover the temperature dependence of various electrical properties was determined and discussed.     

High resolution electron microscopy of bismuth oxides with perovskite layers

Layered bismuth oxides of the general formula (Bi₂O₂)²⁺ (A _n−1B_nO_3n+1)²⁻ whereA = Bi or Ba,B = Ti, Fe, W andn = number of perovskite layers have been investigated by high resolution electron microscopy. Lattice images obtained forn = 1 to 6 members show stacking of (n − 1) perovskite layers sandwiched between dark bands due to the (Bi₂O₂)²⁺ layers. It has been possible to resolve the perovskite layer structures in some of the oxides. A highly ordered structure is observed upto then = 3 member, whereas higher members show superstructures, dislocations and stacking faults arising from the side-stepping of (Bi₂O₂)²⁺ layers as well as ferroelectric domain walls. Contribution No. 73 from Materials Research Laboratory.     

Enhanced piezoelectric properties and electrical resistivity in W/Cr co-doped CaBi2Nb2O9 high-temperature piezoelectric ceramics

W/Cr co-doped Aurivillius-type CaBi₂Nb_2-x(W_2/3Cr_1/3)_xO₉ (CBN) (x?=?0.025, 0.050, 0.075, 0.100, and 0.150) piezoelectric ceramics were prepared by the conventional solid-state reaction method. The crystal structure, microstructure, dielectric properties, piezoelectric properties, and electrical conductivity of these ceramics were systematically investigated. After optimum W/Cr modification, the CBN ceramics showed both high d₃₃ and T_C. The ceramic with x?=?0.1 showed a remarkably high d₃₃ value of ~15 pC/N along with a high T_C of ~931?°C. Moreover, the ceramic also showed excellent thermal stability evident from the increase in its planar electromechanical coupling factor k_p from 8.14% at room temperature to 11.04% at 600?°C. After annealing at 900?°C for 2?h, the ceramic showed a d₃₃ value of 14?pC/N. Furthermore, at 600?°C, the ceramic also showed a relatively high resistivity of 4.9?×?10⁵ Ω?cm and a low tanδ of 9%. The results demonstrated the potential of the W/Cr co-doped CBN ceramics for high-temperature applications. We also elucidated the mechanism for the enhanced electrical properties of the ceramics.     

Focus on the ferroelectric polarization behavior of four-layered Aurivillius multiferroic thin film

The well-saturated ferroelectric hysteresis loops with double remnant polarization up to 50?μC/cm² were obtained in four layered Aurivillius-type multiferroic Bi₅FeTi₃O₁₅ thin film. Pulsed positive-up negative-down polarization measurements demonstrate the intrinsic ferroelectric polarization, which present optimal rectangularity and polarization value. The hysteresis loops measurements with larger frequency range of 0.2–100?kHz indicate stable and ultra-fast switching speed of ferroelectric domains. Persistent retention properties were observed, and they are also independent of the applied electric field. In fatigue test an increased dielectric constant is observed along with the suppression of switchable polarization. Both of them can be restored partly to their original values via the stimulating of high electric field. The block domain switching due to the oxygen vacancies aggregated on domain walls are discussed for those characteristics. It is providing important contributions of domain wall pinning in the polarization degradation of Aurivillius-type ferroelectric films with four layers.     

Room temperature magnetoelectric coupling study in multiferroic Bi4NdTi3Fe0.7Ni0.3O15 prepared by a multicalcination procedure

Single-phase Bi₄NdTi₃Fe_0.7Ni_0.3O₁₅ polycrystalline samples were synthesized following a multicalcination procedure. The sample exhibited multiferroic property at room temperature, which was demonstrated by the ferroelectric (2P_r=8.52 μC/cm², 2E_c=89 kV/cm at applied electric field 110 kV/cm) and magnetic (2M_r=388 m emu/g, 2H_c=689 Oe at applied magnetic field 1.04 T) hysteresis loops. More importantly, magnetoelectric coupling effect is observed from measurements of electrical properties not only under small but also under large electric signal when an external magnetic field is applied. The present results suggest a new candidate for a room temperature multiferroic material with magnetoelectric coupling effect.     

Enhanced piezoelectric properties and low electrical conductivity of Ce-doped Bi7Ti4.5W0.5O21 intergrowth piezoelectric ceramics

New types of Ce-doped Ce_xBi_7-xTi_4.5W_0.5O₂₁ (BTW-BIT-xCe) Aurivillius intergrowth ceramics with high Curie temperatures were synthesized to improve the piezoelectric performances as well as the conduction behaviour, and these ceramics exhibit great potential for high-temperature lead-free piezoelectric applications. The crystal structure, electrical properties and conduction behaviour of BTW-BIT-xCe samples were analysed thoroughly. The XRD patterns combined with Rietveld refinements of the patterns showed that the crystal structure transformed from orthorhombic structure towards pseudo-tetragonal structure with increasing CeO₂ dopant, indicating that a higher symmetry was obtained. The dielectric properties of Ce-doped samples were improved, accompanied by a significant drop in the dielectric loss and a slight decreased Curie temperature (705 °C–683 °C). An enhanced piezoelectric constant d₃₃ of 25.3 pC/N was obtained in BTW-BIT-0.12Ce, which may be attributed to a common decrease in the electrical conductivity and coercive field. Besides, a low electrical conductivity of 2 × 10^-6 S/cm at 540 °C was achieved in the same component owing to a decreased concentration of the oxygen vacancies, which was verified by analyses on XPS spectra. The above results indicate that Ce-doped BTW-BIT samples have great development potential for high temperature piezoelectric applications.     

Aurivillius Oxides Nanosheets-Based Photocatalysts for Efficient Oxidation of Malachite Green Dye

Aurivillius oxides ferroelectric layered materials are formed by bismuth oxide and pseu-do-perovskite layers. They have a good ionic conductivity, which is beneficial for various photo-catalyzed reactions. Here, we synthesized ultra-thin nanosheets of two different Aurivillius oxides, Bi₂WO₆ (BWO) and Bi₂MoO₆ (BMO), by using a hard-template process. All materials were characterized through XRD, TEM, FTIR, TGA/DSC, DLS/ELS, DRS, UV-Vis. Band gap material (E_g) and potential of the valence band (E_VB) were calculated for BWO and BMO. In contrast to previous reports on the use of multi composite materials, a new procedure for photocatalytic efficient BMO nanosheets was developed. The procedure, with an additional step only, avoids the use of composite materials, improves crystal structure, and strongly reduces impurities. BWO and BMO were used as photocatalysts for the degradation of the water pollutant dye malachite green (MG). MG removal kinetics was fitted with Langmuir—Hinshelwood model obtaining a kinetic constant k = 7.81 × 10⁻² min⁻¹ for BWO and k = 9.27 × 10⁻² min⁻¹ for BMO. Photocatalytic dye degradation was highly effective, reaching 89% and 91% MG removal for BWO and BMO, respectively. A control experiment, carried out in the absence of light, allowed to quantify the contribution of adsorption to MG removal process. Adsorption contributed to MG removal by a 51% for BWO and only by a 19% for BMO, suggesting a different degradation mechanism for the two photocatalysts. The advanced MG degradation process due to BMO is likely caused by the high crystallinity of the material synthetized with the new procedure. Reuse tests demonstrated that both photocatalysts are highly active and stable reaching a MG removal up to 95% at the 10th reaction cycle. These results demonstrate that BMO nanosheets, synthesized with an easy additional step, achieved the best degradation performance, and can be successfully used for environmental remediation applications.     

Blue excited photoluminescence of Pr doped CaBi2Ta2O9 based ferroelectrics

Pr³⁺ doped CaBi₂Ta₂O₉ based bismuth layered-structure oxides were synthesized by a simple solid state reaction method. The photoluminescence properties of the samples were investigated by excitation and emission spectra. Photoluminescence excitation spectra show that the samples have broad blue excitation band located at 430-510 nm, which covers the emission wavelength of commercial blue light-emitting diode (LED) chips. Upon the excitation of 450 nm light, a novel red emission centered at 621 nm of Pr doped CaBi₂Ta₂O₉ makes it useful in the white LEDs. In addition, it was also found that the photoluminescence can been improved by partial substituting Sr for Ca. These Pr³⁺ doped CaBi₂Ta₂O₉ based ferroelectrics could possibly be used as a multifunctional material for a wide range of applications, such as integrated electro-optical devices.