Structural and electric properties of Bi2Zn2/3Nb4/3O7 thin films prepared by pulsed laser deposition

Bi₂Zn_2/3Nb_4/3O₇ thin films were deposited on Pt/TiO₂/SiO₂/Si(100) substrates under an oxygen pressure of 10 Pa by pulsed laser deposition. The substrate temperature varied from 500 ^°C to 750 ^°C. Effects of substrate temperature on the crystallinity, microstructure, and electric properties of Bi₂Zn_2/3Nb_4/3O₇ thin films have been systematically investigated. Bi₂Zn_2/3Nb_4/3O₇ thin films are amorphous in nature at a substrate temperature of 500 ^°C. With increase of substrate temperature to 550 ^°C, thin films begin to crystallize. At higher temperature of 750 ^°C, Bi₂O₃ phase can be detected in thin films. However, the crystallized thin films exhibit a cubic pyrochlore structure, not a monoclinic zirconolite structure, which is probably attributed by the composition deviation from the stoichiometric ratio. The resultant Bi₂Zn_2/3Nb_4/3O₇ thin films exhibit the character with high dielectric constant and low loss tangent. The dielectric constant gradually increases with the substrate temperature and reaches a maximum at 700 ^°C. The dielectric constant and loss tangent of the thin films deposited at 700 ^°C are 152 and 0.002 at 10 kHz, respectively. With further increase of substrate temperature to 750 ^°C, the dielectric constant decreases to 128. However, the tunability of the resultant thin films disappears, and the temperature coefficients are positive, which implies a more ordered structure in thin films.     

铁电单晶Pb (Mg1/3Nb2/3)O3-PbTiO3的高场致应变及其在层叠式驱动器中的应用

通过研究(1_x)Pb(Mg_1/3Nb_2/3)O_{3_x}PbTiO3(PMNT)单晶在不同方向、不同组分下高场致应变的特性，确定了〈001〉取向 PMNT单晶（29％≤x≤31%）为制作层叠式驱动器的最佳组分范围，这组分的单晶具有高场致应变、低滞后而且性能较稳定的特点.研究结果表明，在保证应变曲线的线性和低滞后的前提下，将近-2kV/cm的负电场能够运用于〈001〉方向的PMNT晶体上. 40层（每片晶片尺寸为7mm×7mm×0.7mm）PM 关键词： PMNT单晶 场致应变 PMNT驱动器     

First-principles study of the difference in permittivity between Ba(Mg1 / 3Ta2 / 3)O3 and Ba(Mg1 / 3Nb2 / 3)O3

This paper discusses the difference in permittivity at infrared frequencies between Ba(Mg_1/3Ta_2/3)O₃ (BMT) and Ba(Mg_1/3Nb_2/3)O₃ (BMN) based on a first-principles calculation. The permittivity, far-infrared and Raman spectra are successfully computed. Analysis of these results shows that the smaller amplitude of O in the low frequency mode E_u² (BMT), which is caused by the larger polarizability of Ta⁵⁺, is the origin of the smaller permittivity of BMT.     

High electric-field-induced strain of Pb(Mg1/3Nb2/3)O3-PbTiO3 crystals in multilayer actuators

An optimum composition range (29%≤x≤31%) of 〈001〉 oriented (1−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃(PMNT) crystals was ascertained for multilayer actuator applications, which exhibited high-strain and low-hysteresis behavior. A −1.5 kV/cm negative E-field can be applied to PMNT ferroelectric samples with low hysteresis. Forty layer actuators with individual element sizes of 7×7×0.7 mm³ were fabricated under identical processing conditions using two different materials: (1) single crystal PMNT and (2) commercial PZT-SF ceramics. Under free-load conditions, 48 μm displacements can been achieved in PMNT actuators at electric fields ranging from −1.5 to 10 kV/cm, which is more than twice the displacement of the PZT-SF actuators driven from −10 to 10 kV/cm. Under 4 kg loading, the displacements in PMNT stain actuators are decreased to 42.5 μm.     

Polarization switching by stretched exponential functions in 0.7Pb(Mg1/3Nb2/3)O3–0.3PbTiO3

Polarization reversal and domain dynamics have been investigated in 0.7Pb(Mg_1/3Nb_2/3)O₃–0.3PbTiO₃ using a method of current transients. Investigations were performed as a function of applied electric field. The kinetics of the transients have been modelled by a stretched-exponential-type function.     

Vibration Spectra and Structural Characteristics of Ba[(Zn1-x Mg x )1/3Nb2/3]O3 Solid Solutions

Abstract

The Ba[(Zn_1-x Mg _x )_1/3Nb_2/3]O₃ (BZMN, x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) solid solution ceramics were synthesized by the conventional solid-state reaction method. Vibration spectra (Raman spectroscopy and Fourier transform far-infrared reflection [FTIR] spectroscopy) and X-ray diffraction (XRD) were employed to evaluate the correlation between crystal structures and vibration modes of these solid solutions as a function of Zn²⁺ ions replaced by Mg²⁺ ions. Spectroscopic and structural data show sensitivity to the sample structural evolution with Mg²⁺ concentration, and a 1:2 ordered structure appears for Mg-rich samples where x ≥ 0.6. The Ba[(Zn_0.4Mg_0.6)_1/3Nb_2/3]O₃ has a 1:2 ordered monoclinic unit cell, which is distorted by the antiphase tilting of the oxygen octahedra. The phonon modes were assigned, and a correlation of phonon vibrations with the microstructure was found. The position and width of the phonon modes were determined and correlated to the ionic radii, mass, and tolerance factors for the different atoms substituted in the B′-site.     

Microstructure and properties of Pb(Mg1/3Nb2/3)O3–Portland cement composites

Lead magnesium niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN), ceramics particles was mixed with Portland Cement (PC) using a water to cement ratio of 0.50 and PMN content at 40% and 60% by weight to produce 0–3 Pb(Mg_1/3Nb_2/3)O₃–Portland cement (PMN–PC) composites. Microstructure and hydration of the composites were investigated. Calcium silicate hydrate gel can be seen surrounding the PMN particles. Dielectric constant of the composites was found to increase with PMN content. Successful poling of the composites was achieved. Interestingly, SEM micrographs of the PMN40 composite clearly showed calcium silicate hydrate gel (an essential hydration product of Portland cement) surrounding the PMN particles. In PMN60 composite, the gel can also still be seen but of less quantity. This is thought to be due to the increase in the volume ratio of the ceramics where the amount of calcium silicate hydrate gel was reduced in relation to the overall volume.     

Ferroelectric properties of Bi3.25−x/3La0.75Ti3−xNbxO12 films prepared by pulsed laser deposition

Bi₄Ti₃O₁₂ (BiT), Bi_3.25La_0.75Ti₃O₁₂ (BLT), Bi_4−x/3Ti_3−xNb_xO₁₂ (BTN) and Bi_3.25−x/3La_0.75Ti_3−xNb_xO₁₂ (BLTN) thin films have been prepared by pulsed laser deposition. BTN and BLTN films exhibit a maximum in the remanent polarization P_r at a Nb content x=0.018. At this Nb content, the BLTN film has a P_r value (25 μC/cm²) that is much higher than that of BiT and a coercive field similar to that of BiT. The polarization of this BLTN film is fatigue-free up to 10⁹ switching cycles. The high fatigue resistance is mainly due to the substitution of Bi³⁺ ions by La³⁺ ions at the A site and the enhanced P_r arises largely from the replacement of Ti⁴⁺ ions by Nb⁵⁺ ions at the B site. The mechanisms behind the effects of the substitution at the two sites are discussed.     

Effect of Hydrostatic Pressure on the Dielectric Response of Pb(Mg1/3Nb2/3)O3 Relaxor

The effect of hydrostatic pressure on the dielectric response of Pb(Mg_1/3Nb_2/3)O₃ relaxor single crystal was studied. An increase in the dispersion of the dielectric anomaly, characteristic of the relaxors, was observed: pressure-induced downward shift of the temperature T _m of permittivity maximum at 1 kHz amounts to dT _m /dp = ? 3.8 K/100 MPa, whereas that measured at 1 MHz equals ? 3.3 K/100 MPa. Analysis of the dielectric response of the highly polarizable Pb(Mg_1/3Nb_2/3)O₃ shows that hydrostatic pressure results in a decrease of the correlation radius r _c of polar nanodomains, as well as their activation energy.     

SrBi2Ta2O9/Bi4Ti3O12复合铁电薄膜的制备与特性研究

采用溶胶凝胶工艺在p-Si衬底上制备了SrBi₂Ta₂O₉/Bi₄Ti₃O₁₂复合铁电薄膜. 研究了SrBi₂Ta₂O₉/Bi₄Ti₃O₁₂复合薄膜的微观结构与生长行为、铁电性能和疲劳特性. 研究表明: Si衬底Bi₄Ti< 关键词： 2Ta₂O₉')" href="#">SrBi₂Ta₂O₉ 4Ti₃O₁₂')" href="#">Bi₄Ti₃O₁₂ 复合铁电薄膜 溶胶凝胶工艺     

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.     

Electric field effects on the dielectric and acoustic anomalies of Pb[(Mg1/3Nb2/3)0.83Ti0.17]O3 single crystals studied by dielectric and Brillouin spectroscopies

The effect of the electric field on the dielectric and acoustic properties of Pb[(Mg_1/3Nb_2/3)_0.83Ti_0.17]O₃ single crystals was investigated as functions of temperature and the electric field strength. The dielectric constant and the acoustic mode behaviors exhibited typical relaxor behaviors when there was no bias field. The longitudinal acoustic mode showed splitting under a moderate electric field of 1 kV/cm applied along the [001] direction, indicating coexistence of macroscopic/mesoscopic ferroelectric states and relaxor states. Further increase in the electric field up to 2 kV/cm induced a clear ferroelectric phase transition, which became smeared out due to the proximity of the electric field to the critical point. The electric field-temperature phase diagram of Pb[(Mg_1/3Nb_2/3)_0.83Ti_0.17]O₃ was suggested based on the observed field-induced changes in the dielectric and the acoustic properties.     

Enhanced photoluminescence of Sm/Bi co-doped Gd2O3 phosphors by combustion synthesis

Gd₂O₃:Sm³⁺ and Gd₂O₃:Sm³⁺,Bi³⁺ powders were prepared by a combustion method. Their structures were determined using X-ray diffraction. UV-visible absorption and photoluminescence spectra were investigated for Gd₂O₃:Sm³⁺ and Gd₂O₃:Sm³⁺,Bi³⁺ at different annealing temperatures and different doping concentrations. The emission spectra of all samples presented the characteristic emission narrow lines arising from the ⁴G_5/2→⁶H_J transitions (J=5/2, 7/2, and 9/2) of Sm³⁺ ions upon excitation with UV irradiation. The emission intensity of Sm³⁺ ions was largely enhanced with introducing Bi³⁺ ions into Gd₂O₃:Sm³⁺ and the maximum occurred at a Bi³⁺ concentration of 0.5 mol%. The relevant mechanisms were discussed with the sensitization theory by Dexter and the aggregation behavior of Bi³⁺ ions.     

The transverse laser induced thermoelectric voltages in step flow growth （1-x）Pb(Mg1/3Nb2/3)O3-xPbTiO3 thin films

This paper reports that the transverse laser induced thermoelectric voltages (LITV) are observed for the first time in the step flow growth (1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 (PMN-PT,x = 0.20, 0.33, 0.50) thin films deposited on vicinal-cut strontium titanate single crystal substrates. Because lead magnesium niobate-lead titanate is a solid solution of lead magnesium niobate (PMN) and lead titanate (PT), there are two types of signals. One is wide with a time response of a microsecond, and the other superimposed with the wide signal is narrow with a time response of a nanosecond. The transverse LITV signals depend on the ratio of PMN to PT drastically. Under the irradiation of 28-ns pulsed KrF excimer laser with the 248-nm wavelength,the largest induced voltage is observed in the 0.50Pb(Mg1/Nb2/3)O3-0.50PbTiO3 films. Moreover, the effects of film thickness, substrates, and tilt angles of substrates are also investigated.     

Polymorphism in Bi2Sn2O7

Single crystals of Bi₂Sn₂O₇ were grown in a Bi₂O₃ flux. Phase transitions were identified at about 90 and 680° using X-ray, SHG, DSC, dielectric, and optical data. γ-Bi₂Sn₂O₇, which exists above 680°C is centric and cubic with a = 10.73 Å at 700°, and it probably has the ideal pyrochlore structure. β-Bi₂Sn₂O₇, which exists between 680° and about 90°C, is acentric but remains cubic with a = 21.40 Å. α-Bi₂Sn₂O₇, which exists from about 90°C to below room temperature, is acentric and noncubic, probably tetragonal with a = 21.328 and c = 21.545 Å. The α-β transition is first order, and the β-γ transition appears to be second order. Substitutions of Pb²⁺ or Cd²⁺ for Bi³⁺ and of Ga³⁺, Rh³⁺ Sc³⁺, In³⁺, Sb⁵⁺ Nb⁵⁺ or Ta⁵⁺ for Sn⁴⁺ lower the α-β transition temperature.     

Templated Grain Growth of Textured Piezoelectric Ceramics

Crystallographic texturing of polycrystalline ferroelectric ceramics offers a means of achieving significant enhancements in the piezoelectric response. Templated grain growth (TGG) enables the fabrication of textured ceramics with single crystal-like properties, as well as single crystals. In TGG, nucleation and growth of the desired crystal on aligned single crystal template particles results in an increased fraction of oriented material with heating. To facilitate alignment during forming, template particles must be anisometric in shape. To serve as the preferred sites for epitaxy and subsequent oriented growth of the matrix, the template particles need to be single crystal and chemically stable up to the growth temperature. Besides templating the growth process, the template particles may also serve as seed sites for phase formation of a reactive matrix. This process, referred to as Reactive TGG (RTGG), has been used to obtain highly oriented Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃, Sr_0.53Ba_0.47Nb₂O₆, and (Na_1/2Bi_1/2)TiO₃-BaTiO₃. Highly oriented Bi₄Ti₃O₁₂, Sr₂Nb₂O₇, CaBi₄Ti₄O₁₅, Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃, Sr_0.53Ba_0.47Nb₂O₆ and (Na_1/2Bi_1/2)TiO₃-BaTiO₃ ceramics have been produced by TGG. The resulting ceramics show texture levels up to 90%, and significant enhancements in the piezoelectric properties relative to randomly oriented ceramics with comparable densities. For example, piezoelectric coefficients of textured piezoelectrics are from 2 to 3 times higher than polycrystalline ceramics and as high as 90% of the single crystal values. In textured PMN-PT, a low field (< 5 kV/cm) piezoelectric coefficient (d ₃₃) of ～1600 pC/N was obtained with > 0.3% strain (at 50 kV/cm). The high field dielectric and electromechanical properties of textured perovskites are more hysteretic than those of single crystals, probably as a result of clamping by the residual template particles, residual random grains, the presence of non-ferroelectric second phases, and a wide orientation distribution. Lateral clamping of one grain by another may also be an important factor in fiber-textured samples. Means to further improve the quality of texture and thus properties of textured piezoelectric ceramics by TGG are presented.     

Dielectric properties of SrBi2−xPrxNb2O9 ceramics (x=0, 0.04 and 0.2)

SrBi_2−xPr_xNb₂O₉ (x=0, 0.04 and 0.2) ceramics were prepared by a solid state reaction method. X-ray diffraction analysis indicated that single-phase layered perovskite structure ferroelectrics were obtained. A relaxor behavior of frequency dispersion was observed among Pr-doped SrBi₂Nb₂O₉. The degree of frequency dispersion ΔT increased from 0 for x=0-7 °C for x=0.2, and the extent of relaxor behavior γ increased from 0.94 for x=0-1.45 for x=0.2. The substitution of Pr ions for Bi³⁺ ions in the Bi₂O₂ layers resulted in a shift of the Curie point to lower temperatures and a decrease in remanent polarization. In addition, the coercive field 2E_c reduced from 110 kV/cm for an undoped specimen to 90 kV/cm for x=0.2.     

Pb-driven anti-ferroelectric phase in Pb(Mg1/3Nb2/3)O3 : First-principle study

Density functional calculations are used to investigate the role of Pb displacement in the formation of anti-ferroelectric phase in Pb(Mg_1/3Nb_2/3)O₃. Order and disordered supercells, both are used. Through geometry optimization without symmetry imposed, the two supercells are found to be anti-ferroelectric. Displacement of cations are analyzed and it is shown that asymmetry of Pb’s next-nearest B-site shell is probably the reason for anti-parallel displacement of Pb. A–B-site, B-site–O bond distances and O₆ octahedral volumes are also calculated.     

Single-calcination synthesis of pyrochlore-free Pb(Ni1/3Nb2/3)O3-PbTiO3 using a coating method

Pyrochlore-free 0.64Pb(Ni_1/3Nb_2/3)O₃-0.36PbTiO₃ (0.64PNN-0.36PT) powder has been successfully synthesized by only one calcination step using a coating method. The formation of pyrochlore phase is prevented by coating NiCO₃·2Ni(OH)₂·2H₂O on Nb₂O₅ particles. NiCO₃·2Ni(OH)₂·2H₂O-coated Nb₂O₅ powder is prepared by heterogeneous precipitation method. The coating structure is confirmed by transmission electron microscope (TEM) with energy dispersive spectroscope (EDS). Single calcination treatment of the coating powder mixed with appropriate amounts of Pb₃O₄ and TiO₂ powders at 900 °C for 2 h produces the pure-perovskite 0.64PNN-0.36PT powder. The elimination of the pyrochlore phase can be explained in terms of the separating of Pb₃O₄ and Nb₂O₅ by the NiCO₃·2Ni(OH)₂·2H₂O coating layer.     

Piezoelectric properties of PbHfO3–PbTiO3–Pb(Mg1/3Nb2/3)O3 ternary ceramics

(1 – x)Pb(Hf_1–yTi_y)O₃–x Pb(Mg_1/3Nb_2/3)O₃ (x = 0.1 ～ 0.25, y = 0.555) ternary piezoelectric ceramics were prepared using the two‐step precursor method. Morphotropic phase boundary (MPB) compositions, located at x = 0.18 ～ 0.22, were confirmed using X‐ray diffraction and by their dielectric, piezoelectric and ferroelectric properties. The optimum dielectric and piezoelectric properties were achieved for the MPB composition 0.8Pb(Hf_0.445Ti_0.555)O₃–0.2Pb(Mg_1/3Nb_2/3)O₃, with dielectric permittivity ε_r, piezoelectric coefficient d₃₃, planar electromechanical coupling k_p and Curie temperature T_C being on the order of 2800, 680 pC/N, 70% and 276 °C, respectively. Of particular significance is that the new ternary ceramics exhibit comparable piezoelectric and electromechanical properties to commercial PZT5H ceramics, but with much improved T_C, showing a potential for applications at elevated temperature. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)