弛豫铁电体弥散相变的玻璃化特性研究

根据弛豫铁电材料在相变区域的介电弥散行为和玻璃化 液体材料在过冷状态下黏度与温度的行为所共同满足的Vogel-Fulcher 函数关系, 分析了施主替代钛酸钡系列陶瓷的缺陷补偿原理, 通过引入玻璃化液体的构型熵概念, 研究了弛豫铁电材料中钛阳离子缺陷作用势的温度关系, 得到了如下结论: 施主掺杂含量的增加导致了无序度的增加, 钛离子缺陷浓度的增大和平均极性区域尺寸的减小; 在构型熵满足Vogel-Fulcher 函数关系的条件下, 温度越低, 钛离子缺陷作用的范围越大, 极化区域也越大. 缺陷作用的范围随温度的变化导致了弛豫铁电材料的弥散性. 温度下降到一定程度, 冻结效应发生, 介电弥散现象消失.     

等静压和温度诱导的PbLa(Zr,Sn,Ti)O3反铁电陶瓷相变和介电性能研究

研究了等静压和温度诱导掺镧La的Pb(Zr,Sn,Ti)O₃(PLZST)陶瓷材料的铁电反铁电相变、介电压力谱和介电温度谱,研究了温度对压致相变和介电压力谱的影响,结果发现温度使铁电反铁电相变压力降低,介电压力谱具有明显的扩散相变和频率弥散的特点;研究了等静压对介电温度谱的影响,结果表明等静压使铁电反铁电相变温度降低,反铁电顺电相变温度升高.这些现象有利于丰富和拓宽人们对温度和压力诱导的多组元弛豫型铁电体和弛豫型反铁电体扩散相变和弛豫行为的认识和理解. 关键词： 等静压和压致相变 铁电反铁电相变 介电压力谱 介电温度谱     

核壳结构对弛豫铁电体介电行为的影响

介电弥散和介电隔离率的温度非线性关系是弛豫铁电体的主要特征. 通过对掺杂成分以线性梯度递减的核壳结构进行热力学函数分析, 认为核壳结构能够在低温区保持较高的介电常数, 但不能导致介电隔离率与温度的非线性关系. 通过对不同浓度掺杂的铁电体扩散相变的比较, 认为掺杂浓度会影响晶粒掺杂成分的不均匀性, 在较宽的分布条件下会导致介电隔离率与温度的非线性关系. 因而在介电常数的峰值温度区域, 顺电相与铁电相的晶粒共存. 温度变化会影响两相比例及铁电畴的变化, 从而导致弛豫铁电体的介电弥散性. 核壳结构会增大介电弥散性. 铁电陶瓷的掺杂物种类、掺杂物浓度和烧结温度均会影响核壳结构的成分不均匀性和介电弥散性.     

La0.7-x(Sm,Er,Dy)xSr0.3MnO3体系的相分离和渗流相变

通过M-T曲线、M—H曲线、ESR曲线研究了La0.7-x(Sm,Er,Dy)xSr0．3MnO3体系的磁相变．从ESR信号显示,对Er和Dy掺杂在居里温度以上,顺磁相中分离出铁磁团簇,随温度降低呈现渗流相变．稀土锰氧化物的居里温度、宏观磁性和微观磁性不仅取决于A位稀土离子掺杂引起晶格的畸变,而且取决于A位离子掺杂引起的额外磁矩．     

(PbBa)(Zr,Sn,Ti)O_3反铁电/弛豫型铁电相界陶瓷的相变与介电、热释电性质

通过对(Pb087Ba01La002)(Zr06TixSn04-x)O3(004≤x≤020)固溶体的介电和偏压热释电性质的研究发现,当Ti含量004≤x≤007时,材料是反铁电四方相,而当009≤x≤020时,材料向弛豫型铁电体转化.在温度Ti含量相图中,x=009附近形成了反铁电铁电顺电三相共存点(Ttr).该点的相变温度最底;对于004≤x≤007的反铁电四方相,低温下呈现介电弛豫特征,并可被外电场诱导为亚稳铁电态,温度升高时,亚稳铁电→反铁电相变,反铁电→顺电相变引起两个热释电流峰,偏置电场下峰位和峰强均发生移动,在温度电场相图中也形成了铁电反铁电顺电三相点.从复杂化合物纳米相分离的观点和晶格动力学出发,讨论了相变与电学性能随Ti含量(x)和外电场(E)变化的物理机理. 关键词： 反铁电/弛豫型铁电相界 介电性能 偏压热释电性质 铁电-反铁电-顺电三相点     

Si掺杂HfO_2薄膜的铁电和反铁电性质

通过改变Si掺杂量制备出了具有显著铁电和反铁电特征的HfO2纳米薄膜,对其电滞回线、电容-电压和漏电流-电压特性以及物相温度稳定性进行了对比研究.反铁电薄膜的介电系数大于铁电薄膜,在电场加载和减载过程中发生的可逆反铁电-铁电相变导致了双电滞回线的出现,在室温至185℃的测试温度范围内未出现反铁电→顺电相变.在电流-电压特性测量时观察到的负微分电阻效应归因于极化弛豫等慢响应机理的贡献.     

Phase Transition and Oxygen Ion Diffusion in (La1-xLnx)2Mo2O9 (Ln=Nd, Gd, x=0.05-0.25) Using Dielectric Relaxation Method

采用介电弛豫方法研究了氧离子导体(La1-xRex)2Mo2O9(Re=Nd, Gd, x=0.05-0.25)中氧离子扩散和相变行为. 观察到了两个介电损耗峰：第一个峰Pd在600 K附近,第二个峰Ph在720 K左右.Pd峰为弛豫型介电损耗峰,是由氧离子的短程扩散导致的. 随着频率增加,Ph峰基本上不随频率移动,但是峰高随着频率显著的下降.Ph峰表现出非弛豫型的本质,对应于氧离子和氧空位的分布从静态无序到动态无序的转变过程. 随着掺杂浓度的增加,Pd峰和Ph峰的峰高先是增加,在15%的掺杂量达到最高后开始降低. 与此对应,电导率也在此掺杂浓度下出现最大值.     

等静压下0.75Pb（Mg1/3Nb2/3）O3-0.25PbTiO3陶瓷的介电性能研究

研究了等静压对0.75Pb（Mg_1/3Nb_2/3）O₃-0.25PbTiO₃（PMN-25PT）陶瓷介电温谱的影响,PMN-25PT剩余极化随等静压变化和等静压压致相变.结果表明,随着压力增加,PMN-25PT的介电峰值温度T_m降低,/+{dT_m}/-{dP}≈-4℃/kbar,极化弛豫增强;剩余极化随压力增加连续减小;介电常数对压力的依赖关系与对温度场的依赖相似,压力诱导PMN-25PT发生弛豫铁电—顺电相变,相变为宽化的渐变过程,频率色散和极化弛豫更加强烈和普遍. 关键词： 铌镁酸铅-钛酸铅 等静压 介电弛豫 压致相变     

Dy掺杂对Sr2Bi4Ti5O18铁电陶瓷性能的影响

用传统固相烧结法制备了Sr₂Bi_4-xDy_xTi₅ O₁₈(SBDT-x, x=0—0.20)陶瓷样品. x射线衍射分析表明, 微量的Dy掺杂没有影 响Sr₂Bi₄Ti₅O₁₈(SBTi) 原有的层状钙钛 矿结构. 通过研究样品的介电特性, 发现Dy掺杂减小了材料的损耗因子, 降低了样品铁电- 顺电相转变的居里温度. 铁电性能测量结果表明, 随Dy含量的增加, SBDT-x系列样品的剩余 极化先增大, 后减小. 当Dy掺杂量为0.01时, 剩余极化达到最大值, 约为20.1 μC·cm^-2. 掺杂引起剩余极化的变化, 与材料中缺陷浓度、内应力以及晶格畸变程度等因 素有关, 是多种作用机理相互竞争的结果. (Bi₂O₂)²⁺ 层通常被看作是绝缘层和空间电荷库, 对材料的铁电性能起关键作用. 掺杂离子进入(Bi2O₂)²⁺层会导致铁电性能变差. 关键词： 2Bi₄Ti₅O₁₈陶瓷')" href="#">Sr₂Bi₄Ti₅O₁₈陶瓷 Dy掺 杂 铁电性能 居里温度     

弛豫铁电体材料的内耗研究

内耗测量被证明是研究弛豫铁电体中相变的有效方法之一.我们研究了弛豫铁电陶瓷 (1-x%)Pb(Mg1/3Nb2/3)O3-x%PbTiO3 (PMNTx), (0＜x＜33)在低频(0.1 Hz至10Hz)和音频(1 kHz)的内耗.实验表明在铁电微畴的冻结温度出现了一个相变内耗峰和模量的软化,并且随作PbTiO3含量的增加相变逐渐增强,该相变与微畴冻结之间的关系还需作进一步的研究.同时我们还测量到了铁电纳米微畴的反转引起的力学响应,这与其介电响应结果是一致的.     

弛豫铁电体的键能与配位数模型

基于一定浓度的杂质会在钛酸钡型铁电体中导致键能与配位数的高斯型分布原理,利用键能与配位数起伏模型导出了介电峰温与测量频率的关系.当键能和配位数的相对起伏接近时,其关系呈现出一般弛豫铁电体所普遍具有的Vogel-Fulcher函数形式,且冻结温度仅与键能的相对起伏和激活能有关.并由此解释了低掺杂浓度下杂质均匀分布导致弥散性的机理和超过临界浓度时的弛豫铁电性的机理.同时提出,杂质替代对畴的形成和生长所产生的强烈抑制作用及微畴化是实现键能起伏与配位数起伏一致的来源.     

Influence of the A and B vacancies on the dielectric and structural properties of the PLZT 8/60/40 ferroelectric ceramic system

The lanthanum modified lead zirconate titanate (PLZT) ferroelectric ceramics, considering La/Zr/Ti ratio of 8/60/40 and vacancies in A or B sites of the perovskite structure, have been analyzed by using X-ray diffraction, dielectric response, polarized light microscopy and ferroelectric hysteresis. No remarkable differences are observed between samples with A or B vacancies from the X-ray diffraction patterns and ferroelectric hysteresis loops. However, the dielectric measurements have revealed a significant decrease in the maximum values for the real part of the dielectric permittivity and an enhancement of the relaxor behavior in the systems where A vacancies have been considered. On the other hand, the anomalies observed in the temperature dependence of the remanent polarization suggest a frozen out in the dynamic of Nanometric Polar Regions (PNRs) around the same region of temperatures for both samples.     

Effect of Ni doping on ferroelectric and dielectric properties of strontium barium niobate crystals

The influence of Ni doping on the ferroelectric and dielectric properties have been examined in Sr_0.61Ba_0.39Nb₂O₆ (SBN:61) relaxor crystals. The dopants introduced into SBN:61 crystals promote the switching process by reducing the value of threshold nucleation field, and thus coercive field. We present real-time studies of domain nucleation and growth processes in doped SBN:61 by the nematic liquid crystal (NLC) decoration technique. The broad phase transition and low-frequency dielectric dispersion that are exhibited by doped SBN:61 samples have a strong link to the configuration of the ferroelectrics microdomains, which in turn is strongly determined by Ni ions concentration.     

Neutral-ionic phase separation and one-dimensional ferroelectricity in organic relaxors

Microscopic phase segregation by chemical doping and resultant anomalous dielectric response have been investigated for tetrathiafulvalene-p-chloranil complex doped with trichloro-p-benzoquinone ( QCl3). Beyond a critical QCl3 content, the system shows a behavior of relaxor ferroelectrics, as characterized by strong frequency dispersion and a rounded peak shape of gigantic dielectric susceptibility. The relaxor phase arises from one-dimensional ferroelectricity, as evidenced by a diffuse x-ray scattering, in which interchain ferroelectric coupling associated with neutral-ionic transition is interrupted by impurity-generated neutral microclusters.     

Dielectric properties of evaporated films

The evidence for vacancy-pair formation in alkali halide crystals is reviewed. Existing information on the dielectric properties and structure of thin films is discussed with a view to using the high defect concentrations in vacuum-deposited films to confirm vacancy-pair orientation effects. Experimental measurements of the dielectric constant and dissipation factor of evaporated films have been made at room temperature over a range of frequencies from 100 c.p.s. to 100 kc/s. Even under vacuum these films show pronounced losses at low frequencies which are attributed to excess vacancy concentrations. Such losses are contrary to the theory of ideal lattices and are not shown by single crystals.

In spite of the excess defect concentrations no evidence of vacancy-pair orientation has been found. Ageing effects have been observed in all cases, the losses decreasing with time as the defect concentration decreases. In the alkali halides the magnitude of the losses depends on the cation mobility but they decrease at a rate determined by the anion mobility. This leads to a proposed dielectric relaxation mechanism in which individual crystallites form the polarizable units, becoming polarized by migration of the cation vacancies towards one end. The losses decrease as the defects are gradually eliminated by simultaneous condensation of positive and negative vacancies at grain boundaries. This is essential to maintain electrical neutrality and the rate is determined by the diffusion of the slower anion vacancies. The measured rates are in agreement with anion activation energies obtained by tracer methods. These results cannot be explained by vacancy-pair formation even if it is assumed that vacancy pairs can form but are incapable of orientation and hence we must conclude that there is little or no vacancy-pair formation.

Measurements at atmospheric pressure show that moisture has a pronounced effect in all cases, producing dielectric losses which completely obscure the vacancy effects. The changes in dielectric properties during and after adsorption cannot be explained as conductivity effects and are in complete opposition to any modification of the Maxwell-Wagner theory. The ageing effects show that after the initial adsorption, the water molecules migrate over crystallite surfaces to positions where they are more strongly bound and contribute to the dielectric polarization by a form of hindered rotation closely analogous to mechanisms proposed for ice. At these equilibrium sites, H-bonds are frequently formed between the adsorbed molecules and the halide ions of the crystal lattice.     

Dielectric relaxation in LuFeO3 ceramics

LuFeO₃ ceramics were prepared, and the dielectric characteristics were investigated together with the structure. A giant dielectric constant step (8000 at 10 kHz, 7200 at 100 kHz, and 4000 at 1 MHz) very similar to that in LuFe₂O₄ was observed. The dielectric constant dropped quickly when the temperature decreased through a critical temperature which increased significantly when the frequency increased. A very high relaxor-like dielectric peak with strong frequency dispersion was also observed in a higher temperature range. Two obvious corresponding dielectric relaxation peaks were observed on the curve of dielectric loss vs temperature, and all these dielectric relaxations followed the Arrhenius law. The Fe²⁺/Fe³⁺ mixed-valence structure and the oxygen vacancy primarily governed these relxor-like dielectric behaviors. However, the present ceramics are not relaxor ferroelectric.     

Monte Carlo simulation on dielectric relaxation and dipole cluster state in relaxor ferroelectrics

The Ginzburg--Landau theory on ferroelectrics with random field induced by dipole defects is studied by using Monte Carlo simulation, in order to investigate the dipole configuration and the dielectric relaxation of relaxor ferroelectrics. With the increase of random field, the dipole configuration evolves from the long-range ferroelectric order into the coexistence of short-range dipole-clusters and less polarized matrix. The dipole-cluster phase above the transition temperature and superparaelectric fluctuations far below this temperature are identified for the relaxor ferroelectrics. We investigate the frequency dispersion and the time-domain spectrum of the dielectric relaxation, demonstrating the Vogel--Fulcher relationship and the multi-peaked time-domain distribution of the dielectric relaxation.     

Theory of oxidation/reduction-induced valence transformations of metal ion dopants in oxide crystals mediated by oxide-vacancy diffusion: I. Thermodynamic analysis

We consider theoretically valence transformations of doping metal ions in oxide crystals induced by oxidation and reduction obtained by changes in the ambient oxygen partial pressure. Three types of oxygen vacancies are assumed to mediate transformations: neutral, singly ionized, and doubly ionized. We provide thermodynamic equilibrium analyses, yielding concentration relations among the oxygen vacancy, metal ions, holes and electrons as functions of the ambient oxygen pressure. The results suggest that experimental study of different species concentrations at thermodynamic equilibrium as functions of pressure and temperature should allow assessment of various reversible reaction constants controlling the process. In the Part II companion paper, the kinetic (diffusion) characteristics are considered in detail.