Equilibrium Point Defect and Electronic Carrier Distributions near Interfaces in Acceptor-Doped Strontium Titanate

A mathematical model based on Frenkel's theory for charged defect segregation at interfaces is used to calculate the equilibrium grain boundary depletion layer widths and conductivity profiles in acceptor-doped SrTiO₃ ceramics. The calculations examine the effect of oxygen vacancy equilibration during annealing at moderate temperatures (∼1000 K) on the development of interfacial charge that influences grain boundary electrical properties at lower temperatures. Good agreement is demonstrated between the model predictions and experimental results reported in the literature.     

Grain-Boundary Chemistry of Barium Titanate and Strontium Titanate: I, High-Temperature Equilibrium Space Charge

Direct observations using scanning transmission electron microscopy (STEM) of the grain-boundary chemistry of selectively doped SrTiO₃ and BaTiO₃ show the predominant solute segregation in both systems to be that of acceptors (negative effective charge). Appreciable donor segregation is not observed even at lattice concentrations as high as 10 mol%. Donor and acceptor codoped materials show segregation of the acceptor only. The results are consistent with a grain-boundary space-charge distribution consisting of a positive boundary and negative space charge. All grain boundaries examined also show an excess of Ti relative to the A-site cations, suggesting that the positive boundary charge is at least partially accommodated by an excess of Ti ions. The sign and magnitude of the electrostatic potential appear to be remarkably insensitive to changes in lattice defect structure with solute doping. Grain-boundary chemistry appears dominated by space-charge segregation, in contrast with the predictions of recent atomistic simulations which neglect the space-charge potential.     

Resistance Degradation of Iron-Doped Strontium Titanate Investigated by Spatially Resolved Conductivity Measurements

Resistance degradation in perovskites generally is assumed to be caused by stoichiometry variations that occur during high field stress. According to this assumption, distinct conductivity profiles should develop during degradation. In this study, microcontact impedance spectroscopy is used to determine the conductivity profiles in iron-doped strontium titanate after dc stress with a spatial resolution of ∼20 μm. All the features of the characteristic conductivity distributions experimentally observed in single crystals agree with the theoretically predicted distributions and confirm the validity of the stoichiometry polarization model. The degraded samples are concluded to exhibit an oxygen-vacancy enhancement at the cathode and a vacancy depletion at the anode, which leads to a hole–ionic–electron conduction ( p – v – n ) transition of the conduction mechanism. Conductivity measurements at polycrystals revealed subprofiles within single grains, which can be explained by the blocking character of grain boundaries and the resulting accumulation of vacancies on one side of the grain boundaries and a depletion of vacancies on the other side.     

Impedance Spectroscopy Study of Niobium-Doped Strontium Titanate Ceramics

Impedance spectroscopy was used to study the temperature dependence of the resistance and capacitance of niobium-doped strontium titanate ceramics and also to identify the main contributions determining potential applications. Nyquist plots ( Z " versus Z ') show a main contribution in the intermediate-frequency range, with a peak at ∼1 kHz at 500°C. The activation energy of this resistance contribution is close to 1.5 eV. Modulus representations (log M " versus log f ) show a second contribution in the high-frequency range, with a peak at ∼100 kHz at 500°C. This resistance contribution is much smaller, and its activation energy is also lower (close to 0.8 eV). The capacitance of the intermediate-frequency term increases from ∼0.1 μF/m at 700°C to ∼1 μF/m at 425°C. The capacitance values of the high-frequency contribution are also >0.1 μF/m, much higher than expected for the bulk. These contributions might be related to differences between the intergrain interfaces and outer grain shells, as suggested by SEM microstructures with core–shell formations. Representations of 1/ C against temperature suggest a Curie–Weiss law for the main contribution in the intermediate-frequency range, with a T _C of ∼400°C. However, the temperature dependence of the overall dielectric constant measurements (at constant frequency) fail to show a clear maximum, probably due to an additional low-frequency contribution ascribed to the Pt/SrTi_{1− x} Nb _x O_3−δ interface.     

钛酸锶钡微晶玻璃的铈掺杂效应研究

通过X射线光电子能谱、紫外-可见漫反射光谱、傅里叶变换红外光谱和拉曼光谱研究了(Ba,Sr)TiO3微晶玻璃的铈掺杂效应.玻璃体系为BaO-SrO-TiO2-Al2O3-SiO2(Ce摩尔分数为0％、1％、2％、3％).随着Ce摩尔含量增加,Ce在(Ba,Sr)TiO3晶格中的占位从Ce4+取代Ti4+位的形式逐渐变成...     

Grain-Boundary Chemistry of Barium Titanate and Strontium Titanate: II, Origin of Electrical Barriers in Positive-Temperature-Coefficient Thermistors

Scanning transmission electron microscopy (STEM) of positive-temperature-coefficient (PTC) BaTiO₃ thermistors shows that the grain-boundary oxygen content in as-received (oxidatively cooled) materials is slightly enriched compared to quenched samples, and the acceptor-rich space-charge present at high temperatures is retained upon cooling. The defect density of the space charge is approximately equal to the acceptor state density at PTC boundaries determined by electrical measurements. Accordingly, it is proposed that the electrical barrier forms when acceptor defects already segregated in the ionic space charge at high temperature become active interface states when compensating donor defects in the grain-boundary core are oxidized. These acceptor defects appear to be primarily barium vacancies, but need not form upon cooling in the manner proposed by Daniels and Wernicke. Acceptor solutes when present can also contribute to barrier formation through space-charge segregation; the increase in interface state density upon addition of Mn is consistent with the magnitude of the expected segregation.     

Atomic Resolution Analysis of the Defect Chemistry and Microdomain Structure of Brownmillerite-Type Strontium Cobaltite

To investigate the fundamental aspects of vacancy ordering in oxygen-transporting ceramic membranes, we have performed atomic resolution analysis of individual domains in brownmillerite-type SrCoO_3−δ. Electron energy loss spectroscopy indicates that the Co valence state in adjacent planes can be 2+ and 4+. This charge localization is accompanied by oxygen deficiency and the formation of ordered octahedral and tetrahedral coordinated Co sites. At microdomain boundaries, Z -contrast images reveal a structural relaxation of the octahedral site with the reduction of the Co valence state from 4+ to 3+ and the incorporation of extra oxygen vacancies.     

钛酸锶钡陶瓷材料的掺杂改性

钛酸锶钡(BST)是一种重要的具有钙钛矿结构的铁电材料。顺电态下,其介电损耗较小,结构稳定。因此对顺电态下的BST进行掺杂改性是近年来铁电材料的研究热点之一。本文简要介绍了目前国内外科研工作者利用稀土、碱土氧化物进行掺杂时对BST的微观结构、介电损耗、介电常数以及可调率方面的影响。     

Surprising Results of a Study on the Plasticity in Strontium Titanate

Oxides such as SrTiO₃ are expected to fail via brittle fracture at low temperatures. Surprisingly, in the present study, SrTiO₃ single crystals could be plastically deformed in compression in two temperature ranges: from 78 K to ∼1050 K and from 1500 K to 1800 K. SrTiO₃ was brittle at temperatures between these two ranges (∼1050–1500 K). This phenomenon of a ductile–brittle–ductile transition, together with microstructural investigations, suggests that the role of dislocations in the plasticity of ceramics must be reconsidered.     

Effect of Dislocations on Grain Growth in Strontium Titanate

Two series of experiments were done to investigate the effect of dislocations on grain growth in SrTiO₃. In the first series, we observed the growth behavior of a single-crystal plate toward a TiO₂-excess SrTiO₃ powder compact, containing different dislocation densities on two equivalent {100} surfaces. The surface with a higher dislocation density exhibited faster growth, showing interface mobility enhancement by dislocation. In the second series, a polycrystalline SrTiO₃ sample which had been plastically deformed by hot pressing was embedded in a TiO₂-excess SrTiO₃ powder compact, and its growth behavior toward the powder compact was compared with that of a sample without hot pressing. As with a single crystal, the grains with the higher dislocation density in the plastically deformed sample grew faster. In addition, some grains in the plastically deformed sample showed the characteristic of abnormal grain growth. The transmission electron microscopy (TEM) observations on a sintered TiO₂-excess SrTiO₃ showed that the abnormally large grains contained many dislocations while the fine matrix grains contained practically no dislocations. This result suggests that the uneven distribution of dislocations between grains is possibly one of the causes of the abnormal grain growth in polycrystalline SrTiO₃.     

Phase Equilibria in the System Barium Titanate—Strontium Titanate

Phase equilibria in the system BaTiO₃–SrTiO₃ (with 0 to 7 mol% SrTiO₃) were studied at temperatures above 1600°C in air. Quenching experiments were performed using high-purity starting materials, and run products were examined by X-ray diffraction and differential scanning calorimetry to determine phase composition and Sr concentration. Melting involves a binary loop intersected by the invariant reaction hexagonal (Ba, Sr)TiO₃( ss ) ⇌ cubic (Ba, Sr)TiO₃( ss ) + liquid. In contrast with earlier work, these results indicate that there is no depression of the melting point with Sr addition and no congruent melting point in this compositional range.     

钛酸锶钡结构与制备工艺研究进展

钛酸锶钡[(Ba,Sr)TiO3,SBT]是1种重要的电子陶瓷材料,具有高介电常数、低漏电流、高热释电系数,高的介电可调等特性,广泛用于动态随机存储器、热释电探测器、介质移相器等电子元件的制备。综述了钛酸锶钡[(Ba,Sr)TiO3,SBT]的结构和制备工艺研究进展,评述了制备工艺和掺杂等对钛酸锶钡的结构和性能的影响,并指出了钛酸锶钡尚待解决的问题。     

Point Defect Concentrations in Barium Titanate Revisited

An analytic link between the oxygen partial pressure and the concentrations of the point defects for given temperatures and A/B conditions is presented for perovskites. A clear distinction between three different conditions is made. These are the sintering conditions, an intermediate metastable state, and a low-temperature metastable state. The analytical solution for a metastable state resulting from nonequilibrated metal vacancies permits a more accurate and self-consistent approach to calculating the equilibrium constants from conductivity– P (O₂) data. One of the reasons for the higher accuracy is that there is no need to divide the existence regime into subregimes with different approximations to the electroneutrality equation (Brouwer approximation). An excellent fit of the experimental conductivity data to a single function with only two adjustable parameters over all conductivity– P (O₂) space is obtained. The relative importance of frozen-in metal vacancies and foreign acceptors is discussed for BaTiO₃.     

以淀粉为分散剂控制合成纳米钛酸锶研究

研究以钛酸丁酯和氯化锶为原料,采用溶胶-沉淀法合成纳米钛酸锶（SrTiO3）,通过对产物X射线衍射分析,可知NaOH浓度对产物结构具有较大影响;研究不同淀粉添加量与纳米SrTiO3粒度分布之规律,通过改变淀粉配量可有效地控制纳米SrTiO3粒度分布;通过透射电子显微镜和扫描电子显微镜对产品形态和结构进行表征,所得纳米SrTiO3形态比较规则,多数呈球形颗粒,单分散性好,粒径分布为30～80nm。讨论溶胶一沉淀法制备纳米SrTiO3的反应过程,阐明淀粉对纳米SrTiO3粒度调控作用。     

Electrical and Structural Characterization of a Low-Angle Tilt Grain Boundary in Iron-Doped Strontium Titanate

The atomistic structure and electrical properties of a symmetrical 5.4° [001] tilt grain boundary in Fe-doped SrTiO₃ have been investigated, respectively, by means of various transmission electron microscopy (TEM) techniques and impedance spectroscopy. In weak-beam dark-field images, the grain boundary is revealed to consist of a periodic array of dislocations; high-resolution TEM images show that the dislocation cores are separated by regions of strained lattice. The impedance response of the bicrystal has been measured in the frequency range 20 Hz ≤ f ≤ 10⁶ Hz as a function of temperature and oxygen partial pressure. The transport of charge across the array of dislocations that form the grain boundary is strongly hindered. Analysis of the impedance data in terms of a double-Schottky-barrier model yields a space-charge potential that exhibits a weak dependence on temperature and oxygen partial pressure and is ∼0.55 V in the investigated regime.     

Strontium Zirconate and Strontium Titanate Ceramics for High-Voltage Applications: Synthesis, Processing, and Dielectric Properties

The synthesis, processing, and electrical properties of SrZrO₃ and SrTiO₃ materials have been examined. Phase-pure powders of SrZrO₃ and SrTiO₃ materials were synthesized using the Pechini method. Powder processing routes that used water and 2-propanol as carrier fluids were developed to achieve high green densities, which resulted in sintered densities of >99% of the theoretical density. The relative permittivity and average breakdown strength for carefully processed SrZrO₃ were 60 and 40 V/μm; the corresponding values for SrTiO₃ were 400 and 35 V/μm. The higher breakdown strengths suggest that these materials can be used in high-voltage capacitor applications.     

Defect Chemistry and Microstructure of Hydrothermal Barium Titanate

Hydrothermal powders of BaTiO₃ and (Ba,Ca)(Ti,Zr)O₃ contain large amounts of protons in the oxygen sublattice. The proton defects are compensated by vacancies on metal sites. When the powder is annealed, water is released and the point defects disappear in the temperature range of 100°–600°C. Metal and oxygen vacancies combine to small nanometer-sized intragranular pores. At temperatures of >800°C, the intragranular pores migrate to the grain boundaries and disappear. In multilayer ceramic capacitors that have been prepared from hydrothermal powders, the intragranular pores are preferentially collected at the inner electrodes, which results in bloating, cracks, and delamination.     

热水溶液中钛酸锶晶粒的结晶过程

研究了以TiCl4水解得到的H4TiO4胶体作为钛源,在热水溶液中制备SrTiO3晶粒的结晶过程,TEM和XRD结果表明,其结晶过程主要包括3个阶段,第1阶段主要是SrTiO3晶核的形成过程;第2阶段主要是SrTiO3晶粒的配向聚集生长过程;第3阶段主要是SrTiO3晶粒的溶解结晶过程,其中第1阶段的控制步骤为H4TiO4胶体的溶解,第2阶段中晶粒的配向聚集生长在短时间内即可完成,很快进入第3阶段小晶粒的溶解和大晶粒的重结晶过程,该阶段反应速度慢,需要较长时间才能得到结晶完好的晶粒,在热水溶液中以H4TiO4胶体作为钛源制备SrTiO3晶粒关键在于控制结晶过程的第1阶段和第2阶段。     

{111} Twin Formation and Abnormal Grain Growth in Barium Strontium Titanate

Two series of experiments were performed to study the experimental conditions for the formation of {111} twins and related microstructures in barium strontium titanate ((Ba, Sr)TiO₃). In the first series, the phase equilibria in the BaTiO₃–SrTiO₃–TiO₂ system were determined. XRD and WDS analysis, done in the BaTiO₃-rich region, of 45(Ba,Sr)TiO₃–10TiO₂ samples annealed at 1250°C for 200 h in air showed that (Ba,Sr)TiO₃ was in equilibrium with Ba₆Ti₁₇O₄₀ (B₆T₁₇) and Ba₄Ti₁₃O₃₀ phases with strontium solubility (Sr/(Ba + Sr)) of ∼0.02 and 0.20, respectively. In the second series the microstructures of samples consisting of a mixture of (Ba,Sr)TiO₃ and 2.0 mol% TiO₂, were observed after sintering at 1250°C for 100 h in air. {111} twins formed only in the samples with faceted B₆T₁₇ second phase particles, similar to the case of BaTiO₃. In these samples, abnormal grain growth occurred in the presence of the {111} twins. In contrast, no {111} twins formed and no abnormal grain growth occurred in the samples containing second phase particles other than B₆T₁₇. With an increased substitution of strontium for barium, the aspect ratio of abnormal grains containing {111} twin lamellae was reduced. This result was attributed to a reduction in the relative stability of the {111} planes with the strontium substitution.     

钛酸锶缺陷化学研究进展

综述了未掺杂及掺杂钛酸锶的缺陷、钛锶比的影响以及钛酸锶的缺陷化学热力学等方面的研究进展。