Effects of atomic short-range order on the properties of perovskite alloys in their morphotropic phase boundary

The effects of atomic short-range order on the properties of Pb(Zr(1-x)Ti(x))O3 alloy in its morphotropic phase boundary (MPB) are predicted by combining first-principles-based methods and annealing techniques. Clustering is found to lead to a compositional expansion of this boundary, while the association of unlike atoms yields a contraction of this region. Atomic short-range order can thus drastically affect properties of perovskite alloys in their MPB, by inducing phase transitions. Microscopic mechanisms responsible for these effects are revealed and discussed.     

Pb(Zr1-xTix)O3中组分调制诱导的不寻常的铁电相

Pb(Zr1-xTix)O3(PZT)是一种重要的钙钛矿结构铁电固溶体，在其准同型相界处发现单斜相引起研究的热潮，文章报道了作者最近对沿着[100]赝立方方向组分调制的PZT体系的铁电性质的研究结果，发现组分调制导致极化偏离调制方向，在准同型相界附近诱导出新型的铁电三斜相和C型单斜相，以及极高的机电特性，证明偶极相互作用是导致以上行为的主要微观机制。     

(Bi0.5Na0.5)TiO3-Ba(Ti,Zr)O3 陶瓷的电性能研究

采用氧化固相法制备了(1-x)(Bi0.5Na0.5)TiO3-xBa(Ti0.95Zr0.05)O3(BNT-BZT)陶瓷,其中掺入量x的值分别为0,0.04,0.05,0.06,0.07.研究了BNT-BZT体系陶瓷的准同型相界以及陶瓷材料的微观结构和性能之间的关系,并探讨了陶瓷的介电性能和铁电等性能.通过探究Ba(Ti,Zr)O3(BZT)掺杂量对BNT 各性能的影响得出了当掺杂量x=0.05得到结构较为致密,介电,铁电性能较好的样本,对工业化研究和生产有重要的意义     

Effects of strontium on the surface acoustic wave properties of Sm-modified PbTiO3 ceramics

The Sm-modified lead titanate ceramics with a composition of (Pb(0.88-x)Sr(x)Sm(0.08))(Ti(0.98)Mn(0.02))O(3); x = 0.05-0.25 were prepared by conventional mixed-oxide method. Surface acoustic wave (SAW) properties, including phase velocity, electromechanical coupling coefficient and temperature coefficient of frequency, were measured. The experiments successfully showed that Sr additive is helpful to obtain higher phase velocity and high electromechanical coupling coefficient. The SAW properties of our samples (V(p),k(2)) are better than some commercially-made PZT and PT samples.     

Knudsen cell mass spectrometric investigation of the PbO-ZrO(2)-TiO(2) system

Knudsen effusion mass spectrometry (KEMS) was used for direct determination of lead oxide activity as a function of temperature in various regions of the PbO-ZrO(2)-TiO(2) system. From the results, the enthalpy, Gibbs free energy and entropy of formation of PbTiO(3) (PT), PbZrO(3) (PZ) and Pb(Zr,Ti)O(3) (PZT) were evaluated. In addition, the single phase widths of Pb(Zr(0.5)Ti(0.5))O(3) and PbTiO(3) perovskite structures were determined at 1100 K. The reaction rate of PZT synthesis in vacuo was followed by direct measurement of the change of PbO activity with time. Lead oxide activity in stoichiometric Pb(Zr(0.5)Ti(0.5))O(3), PbTiO(3) and Pb(0.968)(Zr(0.5)Ti(0.5))O(2.968) (3% lead deficient) at 850 degrees C was found to be 0.40, 0.45 and 0.1, respectively. PZT, PT and PZ powder samples prepared by a solid state procedure were also measured, all revealing lead deficiency. Copyright 1999 John Wiley & Sons, Ltd.     

改性锆钛酸铅温度诱导相变的热释电性

测量结果显示,Pb_0.99Nb_0.02［(Zr_1-xSn_x)_1-yTi_y］_0.98O₃在温度诱导相变时伴随有正的和负的热释电电流峰.电流的方向与相变类型有如下关系：铁电相向反铁电或顺电相转变时形成正的电流峰,反铁电相向铁电或顺电相转变时形成负的电流峰.按照铁电相与反铁电和顺电相之间存在静电势差的观点,可以很好地解释热释电电流的方向与 关键词： 改性锆钛酸铅化合物 温度诱导相变 热释电性     

Microtexture characterization of PZT ceramics and thin films by electron microscopy

Crystallographic orientations of lead zirconate titanate, Pb(Zr(x),Ti(1-x))O(3) abbreviated PZT, were investigated by the technique of electron backscatter diffraction pattern (EBSP) in the scanning electron microscope (SEM). The samples included unpoled and poled ceramics and a thin film. Several hundreds of crystal orientations in the bulk ceramics and thin films were examined by EBSP and the results were plotted in microtexture pole- and inverse pole-figures for determination of the average and local preferred orientations. In addition, local textures in certain selected regions in PZT ceramics and the misorientations between the nearest neighboring grains were also determined.     

Temperature-dependent structures of proton-conducting Ba(Zr(0.8-x)Ce(x)Y(0.2))O(2.9) ceramics by Raman scattering and x-ray diffraction

In situ temperature-dependent micro-Raman scattering and x-ray diffraction have been performed to study atomic vibration, lattice parameter and structural transition of proton-conducting Ba(Zr(0.8-x)Ce(x)Y(0.2))O(2.9) (BZCY) ceramics (x = 0.0-0.8) synthesized by the glycine-nitrate combustion process. The Raman vibrations have been identified and their frequencies increase with decreasing x as the heavier Ce(4+) ions are replaced by Zr(4+) ions. The main Raman vibrations of Ba(Ce(0.8)Y (0.2))O(2.9) appear near 305, 332, 352, 440 and 635 cm(-1). The X-O ( X=Ce, Zr, Y) stretching modes are sensitive to the variation of Ce/Zr ratio. A rhombohedral-cubic structural transition was observed for x = 0.5-0.8, in which the transition shifts toward higher temperature as cerium increases, except for Ba(Ce(0.8)Y(0.2))O(2.9). A minor monoclinic phase possibly coexists in the rhombohedral matrix for x = 0.5-0.8. The lower-cerium BZCYs (x = 0.0-0.4) ceramics do not exhibit any transition in the region of 20-900?°C, indicating a cubic phase at and above room temperature.     

Polarization rotation via a monoclinic phase in the piezoelectric 92% PbZn(1/3)Nb(2/3)O3-8% PbTiO3

The origin of ultrahigh piezoelectricity in the relaxor ferroelectric PbZn(1/3)Nb(2/3)O3-PbTiO3 was studied with an electric field applied along the [001] direction. The zero-field rhombohedral R phase starts to follow the direct polarization path to tetragonal symmetry via an intermediate monoclinic M phase, but then jumps irreversibly to an alternate path involving a different type of monoclinic distortion. Details of the structure and domain configuration of this novel phase are described. This result suggests that there is a nearby R-M phase boundary as found in the Pb(Ti,Zr)O3 system.     

Pb(Zr_(0.4)Ti_(0.6))O_3电子结构的第一性原理研究

采用基于密度泛函理论的赝势平面波方法计算了Pb(Zr0.4Ti0.6)O3五层超晶胞的顺电相和铁电相的电子结构.由态密度、电子密度和能带结构的计算结果发现顺电相下钛氧八面体Ti-O6和锆氧八面体Zr-O6在铁电相中分裂为由1个O1离子和4个O2离子组成的金字塔结构Ti-O5和Zr-O5;与顺电相相比,铁电相中钛离子的3d电子和氧离子的2p电子存在更强的轨道杂化,这种杂化降低了离子间的短程排斥力,使得具有铁电性的四方结构更为稳定,而且钛离子与氧离子的相互作用对于铁电相Pb(Zr0.4Ti0.6)O3沿c轴自发极化的贡献大于锆离子与氧离子的相互作用;由电子密度的分布可推断立方结构的Pb-O键呈现离子键特征,而铁电相下Pb-O键则有较大的共价成分,铅离子与氧离子的这种轨道杂化对Pb(Zr0.4Ti0.6)O3的铁电性起重要作用.所得结果对深入理解Pb(Zr0.4Ti0.6)O3铁电性的微观机理具有参考价值.     

Single crystal study of competing rhombohedral and monoclinic order in lead zirconate titanate

Neutron diffraction data obtained on single crystals of PbZr(1-x)Ti(x)O3 with x=0.325 and x=0.460, which lie on the pseudorhombohedral side of the morphotropic phase boundary, suggest a coexistence of rhombohedral (R3m/R3c) and monoclinic (Cm) domains and that monoclinic order is enhanced by Ti substitution. A monoclinic phase with a doubled unit cell (Cc) is ruled out as the ground state.     

Can an electric field induce an antiferroelectric phase out of a ferroelectric phase?

It has been widely accepted that electric fields favor the ferroelectric phase with parallel electric dipoles over the antiferroelectric phase. With detailed measurements in polycrystalline ceramics of Pb(0.99)Nb(0.02[(Zr(0.57)Sn(0.43)(1-y)Ti(y)](0.98)O(3), we demonstrate in this Letter that electric fields can induce an antiferroelectric phase out of a ferroelectric phase, i.e., trigger an apparently unlikely ferroelectric-to-antiferroelectric phase transition. We suggest that it is caused by the volume contraction from the converse piezoelectric effect at the coercive field with a reversed polarity.     

Induced Phase Transition in PbMg1/3Nb2/3O3–xPb(Zr0.53Ti0.47)O3 Transparent Ceramics

Physics of the Solid State - Time dependences of permittivity and optical transmission in the Pb(Mg1/3Nb2/3)O3–xPb(Zr0.53Ti0.47)O3 (x = 16, 23, and 33%) transparent ferroelectric ceramics are...     

Electronic structure of charge- and spin-controlled Sr(1-(x+y))La(x+y)Ti(1-x)Cr(x)O3

We present the electronic structure of Sr(1-(x+y))La(x+y)Ti(1-x)Cr(x)O3 investigated by high-resolution photoemission spectroscopy. In the vicinity of the Fermi level, it was found that the electronic structure was composed of a Cr 3d local state with the t(2g)3 configuration and a Ti 3d itinerant state. The energy levels of these Cr and Ti 3d states are well interpreted by the difference of the charge-transfer energy of both ions. The spectral weight of the Cr 3d state is completely proportional to the spin concentration x irrespective of the carrier concentration y, indicating that the spin density can be controlled by x as desired. In contrast, the spectral weight of the Ti 3d state is not proportional to y, depending on the amount of Cr doping.     

Phase diagram of pb(Zr,Ti)O3 solid solutions from first principles

A first-principles-derived scheme that incorporates ferroelectric and antiferrodistortive degrees of freedom is developed to study finite-temperature properties of Pb(Zr1-xTix)O3 solid solution near its morphotropic phase boundary. The use of this numerical technique (i) resolves controversies about the monoclinic ground state for some Ti compositions, (ii) leads to the discovery of an overlooked phase, and (iii) yields three multiphase points that are each associated with four phases. Additional neutron diffraction measurements strongly support some of these predictions.     

Quantitative electron energy-loss spectroscopy (EELS) analyses of lead zirconate titanate

Electron energy-loss spectroscopy (EELS) analyses have been performed on a sol-gel deposited lead zirconate titanate film, showing that EELS can be used for heavy as well as light element analysis. The elemental distributions within the sol-gel layers are profiled using the Pb N(6,7)-edges, Zr M-edges, Ti L-edges and O K-edge. A multiple linear least squares fitting procedure was used to extract the Zr signal which overlaps with the Pb signal. Excellent qualitative information has been obtained on the distribution of the four elements. The non-uniform and complementary distributions of Ti and Zr within each sol-gel deposited layer are observed. The metal:oxygen elemental ratios are quantified using experimental standards of PbTiO(3), PbZrO(3), ZrO(2) and TiO(2) to provide relevant cross-section ratios. The quantitative results obtained for Ti/O and Pb/O are very good but the Zr/O results are less accurate. Methods of further improving the results are discussed.     

Energy harvesting of PZT/PMMA composite flexible films

Polymer/lead zirconate titanate {[Pb(Zr_x, Ti_1-x)O₃], PZT, x = 0.40} flexible composite films are prepared by solvent evaporation technique. Carbon tape used as a top and bottom electrodes for fabricating flexible PZT composite films. The phase purity and functional groups of PZT and polymer humps are confirmed by XRD and FTIR respectively. XPS analysis showed that PMMA contains carbon (C) and oxygen (O). Carbon (C), oxygen (O), lead (Pb), zirconium (Zr) and titanium (Ti) are present in PZT/PMMA composite films. The chemical states of Pb, Zr and Ti ions are 2⁺, 4⁺ and 4⁺ respectively confirmed by XPS. The higher forefinger bending motion of the film is found to reveal greater output voltage (5.2 V) than the output voltage (1.6 V) for slight bending motion of the forefinger. Therefore, based on the results human mechanical forces induce compressive stress on PZTs ferroelectric based composite films and are excellent candidate for energy harvester.     

铁掺杂四方、三方两相共存PZN-PZT陶瓷的Raman散射分析

Raman散射常用于研究温度变化时铁电体的各种相变,如铁电-顺电相变等,但是,利用Raman散射研究掺杂诱导的相变并不常见。本文采用Raman散射研究了铁掺杂Pb(Zn1/3Nb2/3)0.2(Zr0.5Ti0.5)0.8O3(PZN-PZT)铁电陶瓷中三方-四方共存现象。通过分析四方相E(3TO)和A1(3TO)模式与三方相Rl模式,确定了铁掺杂对PZN-PZT陶瓷中三方-四方共存结构的影响。这一结果,得到了XRD相分析的验证。因此,通过对Raman散射中三方-四方振动模式的分析,可以表征掺杂诱导的PZT基陶瓷中三方-四方相结构变化趋势。     

Structure and polarization in the high Tc ferroelectric Bi(Zn,Ti)O3-PbTiO3 solid solutions

Theoretical ab initio and experimental methods are used to investigate the [Bi(Zn1/2Ti1/2)O3]x[PbTiO3]1-x solid solution. We find that hybridization between Zn 4s and 4p and O 2p orbitals allows the formation of short, covalent Zn-O bonds, enabling favorable coupling between A-site and B-site displacements. This leads to unusually large polarization, strong tetragonality, and an elevated ferroelectric to paraelectric phase transition temperature.     

Non-magnetic impurity induced magnetism in rutile TiO2:K compounds

Recent ab initio studies have theoretically predicted room temperature ferromagnetism in several oxide materials of the type AO(2) in which the cation A(4+) is substituted by a non-magnetic element of the 1 A column. Our purpose is to address experimentally the possibility of magnetism in Ti(1-x)K(x)O(2) compounds. The samples have been synthesized via the solid state route method at equilibrium. Our study has shown that Ti(1-x)K(x)O(2) is thermodynamically unstable and leads to a phase separation, in contradiction with the hypothesis of ab initio calculations. In particular, the crystalline TiO(2) grains appear to be surrounded by K-based phase. The oxidization state of the Ti ion is found to be in Ti(4+) as confirmed from the x-ray photoelectron spectra measurement. Nevertheless, K:TiO(2) compounds exhibit weak paramagnetism with the highest magnetic moment of ~0.5 μ(B) K(-1) but no long-range ferromagnetic order. The observed moment in these compounds remains much smaller than the predicted moment of 3 μ(B) by ab initio calculation. The apparent contradictions between our experiments and first-principles studies are discussed.