Structure refinement of large domain relaxors in the Pb(Mg1/3Ta2/3)O3-PbZrO3 system

The relaxor ferroelectric compound Pb(Mg_0.3Ta_0.6Zr_0.1)O₃ (PMT-PZ) was studied by X-ray, neutron and electron diffraction and transmission electron microscopy in the as-sintered and annealed states. The as-sintered sample was comprised of nanometer-sized 1:1 chemically ordered domains dispersed in a disordered matrix. After annealing at 1325°C the domain size increased to ∼30 nm and the degree of order exceeded 95% in terms of the volume fraction of the ordered domains, yet the sample retained its diffuse, frequency dependent relaxor characteristics. Refinements of the chemically ordered structure using the Rietveld analysis revealed that the octahedral (B) site occupancies were in excellent agreement with a “random site” model for the chemical ordering. In this charge-balanced model for the 1:1 ordered Pb(β′_1/2β″_1/2)O₃ structure the Ta cations predominantly occupy the β″ site, while the β′ site is populated by a random distribution of the Mg, Zr and remaining Ta cations. Large temperature factors for Pb and O atoms are observed in both as-sintered and annealed samples, indicating localized displacements of the Pb and O atoms. The mixed occupancy of the β′ position appears to be responsible for the relaxor characteristics in the dielectric response in spite of the growth of the chemical domains.     

Ferroelectric relaxor behaviour in Pb(Fe0.5Ta0.5)O3

The relaxor ferroelectric lead iron tantalate, Pb(Fe_0.5Ta_0.5)O₃ (PFT) is synthesized by Coulombite precursor method. The X-ray diffraction pattern of the sample at room temperature shows a cubic phase. The field dependence of dielectric response is measured in a frequency range 0.1 kHz — 1 MHz and in a temperature range from 173–373 K. The temperature dependence of permittivity (ɛ′) shows broad maxima at various frequencies. The frequency dependence of the permittivity maximum temperature (T _m ) has been modelled using Vogel-Fulcher relation.      

Dielectric and impedance measurements on (1−x)Ba(Fe1/2Ta1/2)O3-xBa(Zn1/3Ta2/3)O3 ceramics

In this work, ((1−x)Ba(Fe_1/2Ta_1/2)O₃-xBa(Zn_1/3Ta_2/3)O₃), ((1−x)BFT-xBZT) ceramics with x = 0.00–0.12 were synthesized by the solid–state reaction method. X-ray diffraction data revealed that both the powders and ceramics were of a pure-phase cubic perovskite structure. All ceramics showed large dielectric constants. For the x = 0.12 sample, a very high dielectric constant (>20,600) was observed. A lowering in the dielectric loss compared to pure BFT ceramics was observed with the BZT addition. The impedance measurements indicated that BZT has a strong effect on the bulk grain and grain boundary resistance of BFT ceramics. These results are in agreement with the measured dielectric properties. Based on dielectric and impedance results, (1−x)BFT-xBZT ceramics could be of great interest for high performance dielectric materials applications due their giant dielectric constant behavior.     

Structural and electrical impedance study of Pb(Sr1/3Nb2/3)O3

Lead-based ceramic Pb(Sr_1/3Nb_2/3)O₃ (PSN) is prepared by the columbite precursor method and structurally characterized using XRD. The X-ray diffraction shows a perovskite structure with cubic pyrochlore phase. Detailed studies of ε′ and ε″ of the compounds show that the compounds exhibit dielectric anomaly. Impedance spectroscopy is used to characterize the electrical behaviour. Results indicate that the relaxation mechanism of the material is temperature dependent and has dominant bulk contribution in different temperature ranges. Modulus spectroscopic data were used to gain an insight into the electrical properties of the samples and with a view to observe the relaxations in them. Frequency dependence dielectric permittivity shows typical Debye-type dielectric dispersion. Temperature-dependent DC resistivity shows that resistance decreases with the increase in temperature and follows Arrhenius behaviour in different temperature regions.     

Phase diagram of the relaxor (1−x)Pb(Zn1/3Nb2/3)O3-xPbTiO3 investigated by dielectric and Raman spectroscopies

Lead zinc niobate-lead titanate[(1−x)Pb(Zn_1/3Nb_2/3)O₃-xPbTiO₃] (PZN-PT) crystals with x=4.5% and x=12% have been investigated using dielectric and Raman measurements over a range of temperatures. Above room temperature, dielectric measurements show that both compositions exhibit structural phase transitions according to the phase diagram proposed by Kuwata et al. [Ferroelectrics 387 (1981) 579]. Below room temperature, an anomaly at around 180 K for the x=12% sample is observed, suggesting another phase transition. Raman measurements are used to study all phase transitions.     

Phase transition, structural and electrical properties of Pb(Zn1/3Nb2/3)O3-doped Pb(Ni1/3Nb2/3)O3-PbTiO3 ceramics prepared by solid-state reaction method

Phase pure perovskite (1−x−y)Pb(Ni_1/3Nb_2/3)O₃-xPb(Zn_1/3Nb_2/3)O₃-yPbTiO₃ (PNN-PZN-PT) ferroelectric ceramics were prepared by conventional solid-state reaction method via a B-site oxide mixing route. The PNN-PZN-PT ceramics sintered at the optimized condition of 1185 °C for 2 h exhibit high relative density and rather homogenous microstructure. With the increase of PbTiO₃ (PT) content, crystal structure and electrical properties of the synthesized PNN-PZN-PT ceramics exhibit successive phase transformation. A morphotropic phase boundary (MPB) is supposed to form in (0.9−x)PNN-0.1PZN-xPT at a region of x=32-36 mol% confirmed by X-ray diffraction (XRD) measurement and dielectric measurement. The MPB composition can be pictured as providing a “bridge” connecting rhombohedral ferroelectric (FE) phase and tetragonal one since crystal structure of the MPB composition is similar to both the rhombohedral and tetragonal lattices. Dielectric response of the sintered PNN-PZN-PT ceramics also exhibits successive phase-transition character. 0.64PNN-0.1PZN-0.26PT exhibits broad, diffused and frequency dependent dielectric peaks indicating a character of diffused FE-paraelectric (PE) phase transition of relaxor ferroelectrics and 0.40PNN-0.1PZN-0.50PT exhibits narrow, sharp and frequency independent dielectric peaks indicating a character of first-order FE-PE phase transition of normal ferroelectrics. The FE-PE phase transition of 0.56PNN-0.1PZN-0.34PT is nearly first-order with some diffused character, which also exhibits the largest value of piezoelectric constant d₃₃ of 462pC/N.     

Photoluminescence investigations on the nanoscale phase transition in Pb(Mg1/3Nb2/3)O3

The temperature dependence of the photoluminescence spectra of the relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃ has been reported. The temperature behaviours of the 1.57, 1.67 and 1.73 eV bands indicate a phase transition at 110 K. This is attributed to a structural phase transition in the charged nanoshell. Analysis of the temperature dependence of 1.67 eV band intensity with a thermal quenching model indicated the existence of a phonon mode at 1153 cm⁻¹. This mode is identified in the Raman spectra measurement. The intensity of the 1.73 eV band showing an anomalous behaviour at 210 K is attributed to a transition from a crystalline phase to an amorphous phase in the charged nanoshell.     

Optical and structural studies on Ba(Mg1/3Ta2/3)O3 thin films obtained by radiofrequency assisted pulsed plasma deposition

Single-phase Ba(Mg_1/3Ta_2/3)O₃ thin films were prepared by radiofrequency plasma beam assisted pulsed laser deposition (RF-PLD) starting from a bulk ceramic target synthesized by solid state reaction. Atomic force microscopy, X-ray diffraction and spectroscopic ellipsometry were used for morphological, structural and optical characterization of the BMT thin films. The X-ray diffraction spectra show that the films exhibit a polycrystalline cubic structure. From spectroscopic ellipsometry analysis, the refractive index varies with the thin films deposition parameters. By using the transmission spectra and assuming a direct band to band transition a band gap value of ≈4.72 eV has been obtained.     

Ferroelectric properties of bilayer structured Pb(Zr0.52Ti0.48)O3/SrBi2Ta2O9 (PZT/SBT) thin films on Pt/TiO2/SiO2/Si substrates

Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films with large remanent polarization and SrBi₂Ta₂O₉ (SBT) thin films with excellent fatigue-resisting characteristic have been widely studied for non-volatile random access memories, respectively. To combine these two advantages_, bilayered Pb(Zr_0.52Ti_0.48)O₃/SrBi₂Ta₂O₉ (PZT/SBT) thin films were fabricated on Pt/TiO₂/SiO₂/Si substrates by chemical solution deposition method. X-ray diffraction patterns revealed that the diffraction peaks of PZT/SBT thin films were completely composed of PZT and SBT, and no other secondary phase was observed. The electrical properties of the bilayered structure PZT/SBT films have been investigated in comparison with pure PZT and SBT films. PZT/SBT bilayered thin films showed larger remanent polarization (2P_r) of 18.37 μC/cm² than pure SBT and less polarization fatigue up to 1 × 10⁹ switching cycles than pure PZT. These results indicated that this bilayered structure of PZT/SBT is a promising material combination for ferroelectric memory applications.     

Structural and electrical behavior of Pb(Mg1/4Cd1/4Mo1/2)O3 ceramics

Preliminary X-ray structural analysis of polycrystalline Pb(Mg_1/4Cd_1/4Mo_1/2)O₃ ceramics, prepared by a solid-state reaction technique, provides single-phase orthorhombic structure at room temperature. Detailed dielectric studies of the material as a function of temperature reveal a sharp phase transition at temperature T_c=49°C obeying Curie-Weiss behavior. Scanning electron microscope (SEM) studies of the sample show the uniform distribution of grains in the samples. A dielectric anomaly and ferroelectric phase transition observed at 49°C was supported by polarization studies. The activation energy of the sample was calculated from the dielectric data. The variation of dc resistivity with temperature suggests that the compound behaves as a negative temperature coefficient resistor (NTCR).     

Phase transformation in (0.90−x)Pb(Mg1/3Nb2/3)O3-xPbTiO3-0.10PbZrO3 piezoelectric ceramic: X-ray diffraction and Raman investigation

Piezoelectric ceramics with compositions of (0.90−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃-0.10PbZrO₃, x=0.28, 0.31, 0.34, 0.37, 0.40 and 0.43, were prepared using the conventional columbite precursor method, and their structural phase transformation and piezoelectric behaviors near the morphotropic phase boundary (MPB) have been systematically investigated as a function of PbTiO₃ content. X-ray diffraction (XRD) results demonstrate that the structure of the ceramics experiences a gradual transition process from rhombohedral phase to tetragonal phase with the increasing of PbTiO₃ content, and that compositions with x=0.34-0.40 lie in the MPB region of this ternary system. A Raman spectra investigation of the ceramic samples testified to the transformation process of rhombohedral phase to tetragonal phase by comparing the relative intensities of tetragonal E(2TO₁) mode and rhombohedral phase R_h mode. The structure information was also correlated to the parabola change of the piezoelectric constant; the maximum piezoelectric constants were obtained near the MPB region.     

DIELECTRIC RELAXATION BEHAVIOR OF CERAMICS IN THE Pb(Zn1/3Nb2/3)O3-BaTiO3-PbTiO3 SYSTEM

The dielectric properties of ceramics in Pb(Zn_1/3Nb_2/3)O₃-BaTiO₃-PbTiO₃ system were characterized using dielectric-temperature spectra. A spontaneous (zero field) relaxor-normal ferroelectric tran sition was observed for tetragonal rich compositions. A significant hysteresis effect accompanied by this transition, similar to first-order phase transition of normal ferroelectrics. This behavior was different from that of other relaxors, in which such transitions occurred only under a biased dc field. This observation was explained in terms of a thermally driven transformation from an ensemble of polar microregions to normal long-range ferroelectric state (micro-macro domain transition), which was attributed to the internal field resulting from the tetragonal strain.     

The impedance spectroscopic study and dielectric relaxation in A(Ni1/3Ta2/3)O3 [A=Ba,Ca and Sr]

We present the results of impedance spectroscopic study with its analytical interpretations in the framework of electric modulus formalism for Barium Nickel Tantalate Ba(Ni_1/3Ta_2/3)O₃ (BNT), Calcium Nickel Tantalate Ca(Ni_1/3Ta_2/3)O₃ (CNT) and Strontium Nickel Tantalate Sr(Ni_1/3Ta_2/3)O₃ (SNT) synthesized by the solid-state reaction technique. The results of powder X-ray diffraction study reveal that BNT and SNT crystallize in cubic structure with lattice parameter a=4.07 Å and 3.98 Å respectively, whereas CNT crystallizes in monoclinic structure having lattice parameters, a=5.71 Å, b=13.45 Å and c=5.47 Å with β=118.3°. The logarithmic angular frequency dependence of the real part of complex dielectric permittivity and loss tangent as a function of temperature indicate significant dielectric relaxation in the samples, which have been explained by the Debye theory. The frequency dependence of the loss peak and the imaginary part of electrical modulus are found to obey the Arrhenius law. The relaxation mechanism of these samples is modeled by the Cole–Cole equation. This confirms that the polarization mechanism in BNT, CNT and SNT is due to the bulk effect arising in semiconductive grains. The scaling behavior of imaginary part of electric modulus M″ suggests that the relaxation describes the same mechanism at various temperatures but relaxation frequency is strongly temperature dependent. The normalized peak positions of tan δ/tan δ_m and M″/M″_m versus log ω for BNT, CNT and SNT do not overlap completely and are very close to each other. These indicate the presence of both long-range and localized relaxation. Due to their high dielectric constant and low loss tangent, these materials may find several technological applications such as in capacitors, resonators, filters and integrated circuits.     

Epitaxial growth and structural characterization of Pb(Fe1/2Nb1/2)O3 thin films

We have grown lead iron niobate thin films with composition Pb(Fe_1/2Nb_1/2)O₃ (PFN) on (0 0 1) SrTiO₃ substrates by pulsed laser deposition. The influence of the deposition conditions on the phase purity was studied. Due to similar thermodynamic stability spaces, a pyrochlore phase often coexists with the PFN perovskite phase. By optimizing the kinetic parameters, we succeeded in identifying a deposition window which resulted in epitaxial perovskite-phase PFN thin films with no identifiable trace of impurity phases appearing in the X-ray diffractograms. PFN films having thicknesses between 20 and 200 nm were smooth and epitaxially oriented with the substrate and as demonstrated by RHEED streaks which were aligned with the substrate axes. X-ray diffraction showed that the films were completely c-axis oriented and of excellent crystalline quality with low mosaicity (X-ray rocking curve FWHM?0.09°). The surface roughness of thin films was also investigated by atomic force microscopy. The root-mean-square roughness varies between 0.9 nm for 50-nm-thick films to 16 nm for 100-nm-thick films. We also observe a correlation between grain size, surface roughness and film thickness.     

Synthesis and structural characterization of perovskite 0.65Pb(Mg1/3Nb2/3)O3-0.35PbTiO3 nanotubes

We report the synthesis and structural characterization of 0.65Pb(Mg_1/3Nb_2/3)O₃-0.35PbTiO₃ (PMN-PT) nanotubes prepared by a novel sol-gel template method. X-ray diffraction (XRD) and selected-area electron diffraction (SAED) investigations demonstrated that the postannealed (650 °C for 1 h) PMN-PT nanotubes were polycrystalline with perovskite crystal structure. The field emission scanning electron microscope (FE-SEM) shows that as prepared PMN-PT nanotubes were hollow with diameter to be about 200 nm. High resolution transmission electron microscope (HRTEM) analysis confirmed that the obtained PMN-PT nanotubes made up of nanoparticles (10-20 nm) which were randomly aligned in the nanotubes. Energy-dispersive X-ray spectroscopy (EDX) analysis confirmed the stoichiometric 0.65Pb(Mg_1/3Nb_2/3)O₃-0.35PbTiO₃. The possible formation mechanism of PMN-PT nanotubes was proposed at the end.     

Low-frequency dielectric dispersion and magnetic properties of La,Gd modified Pb(Fe1/2Ta1/2)O3 multiferroics

Pb(Fe_1/2Ta_1/2)O₃ (PFT) modified by rare-earth (La and Gd) ions has been synthesized in a single phase using a double-stage synthesis (i.e., Columbite) technique. Scanning electron micrographs (SEM) of the pellet samples have shown a significant change in their grain size and uniform distribution of Gd/La at the Fe-sites. The room temperature X-ray structural analysis shows that the reported cubic (or tetragonal) structure of PFT has been distorted to a monoclinic system on substitution of La/Gd at the Fe-site. Detailed studies of dielectric properties of the above compound on La/Gd substitution have shown strong dielectric dispersion at low frequency (i.e. relaxor behavior) with drastic change in transition temperature. Magnetic characterization shows that though the PFT sample displays an antiferromagnetic transition at ∼150 K, the rare-earth ions-substituted samples do not. Furthermore, temperature dependence of magnetization measurements shows that spin glass transition observed in PFT at low temperatures (5–20 K) does not exist in the La and Gd substituted PFT. Doping of Gd in PFT increases the sample magnetization, especially at low temperature.     

铁电磁体Pb(Fe1/2Nb1/2)O3的磁电性能研究

对铁电磁体Pb(Fe_1/2Nb_1/2)O₃单晶样品中的 介电和磁性能进行了研究. 认为在其反铁磁相变点观察到的介电常数和损耗的异常来自于自发极化序和自旋序的相互作用 引起的磁电耦合. 磁矩与温度的关系曲线在Nel点以下的低温段呈上升趋势，测得的磁滞 回线证明有弱铁磁性出现. 对铁电磁体磁电相互作用的Monte Carlo模拟得到与实验类似的 结果. 关键词： 铁电磁体 1/2Nb_1/2)O₃')" href="#">Pb(Fe_1/2Nb_1/2)O₃ 磁电耦合 Monte Carlo模拟     

Magnetic ordering and instability investigation of multiferroic Pb(Fe2/3W1/3)O3 ceramics by microwave dielectric spectroscopy

The microwave dielectric and magnetic properties of Pb(Fe_2/3W_1/3)O₃ multiferroic ceramics were investigated. A dielectric dispersion occurring in the frequency range 100 MHz-3 GHz and in a broad temperature range showed itself to be a powerful tool to detect magnetostrictive effects. The experimental results revealed the following remarkable features: the temperature dependence of f_R (characteristic frequency) and the dielectric strength Δε (characteristic of the dispersion) enabled us to identify not only the para-ferroelectric (T_C≈180 K) but also the para-antiferromagnetic (T_N≈340 K) phase transitions, while magnetic measurements revealed the para-antiferromagnetic ordering and a weak superexchange interaction (T_N2∼15 K). Additionally, both characterizations confirmed the existence of structural or magnetic instabilities around 250 K.     

Effect of different annealing methods on ferroelectric properties of 0.95Pb(Sc0.5Ta0.5)O3-0.05PbTiO3 thin films

0.95Pb(Sc_0.5Ta_0.5)O₃-0.05PbTiO₃ thin films were prepared on LaNiO₃/SiO₂/Si substrate by radio frequency magnetron sputtering, and the films were annealed subsequently with repeated many times by two approaches: normal one-step rapid thermal annealing and innovative two-steps rapid thermal annealing. X-ray diffraction demonstrates that all the films were preferred (1 0 0) oriented and an appropriate repeat of annealing process can enhance perovskite phase of the films. Scanning electron microscopy suggests that the films treated by two-steps rapid thermal annealing show crack-free, uniform size grains and dense microstructure. Measurement of remnant polarization and leakage current dependence of electric field confirms that the films treated by two-steps rapid thermal annealing exhibit better ferroelectric properties than the films treated by one-steps rapid thermal annealing. The results reveal that microstructure plays an important role in enhanced ferroelectric properties of the 0.95Pb(Sc_0.5Ta_0.5)O₃-0.05PbTiO₃ thin films.     

Electrical characteristics and low-temperature sintering of BiFeO3-modified Pb(Zr,Ti)O3–Pb(Fe2/3W1/3)O3–Pb(Mn1/3Nb2/3)O3 ceramics with ZnO addition

Effects of ZnO addition on electrical properties and low-temperature sintering of BiFeO₃-modified Pb(Zr,Ti)O₃–Pb(Fe_2/3W_1/3)O₃–Pb(Mn_1/3Nb_2/3)O₃ were investigated. The investigations revealed that the sintering temperature can be decreased to 950 °C, and the favorable properties were obtained with 0.10 wt% ZnO added ceramics. The electrical properties were as follows: d₃₃ = 313 pC/N, K_p = 0.56, tan δ = 0.0053, ε_r = 1407 and T_c = 295 °C, which showed that this system was a promising material for the multilayer devices application.