Synthesis and Characterization of PZT Fibers via Sol-Gel

A fiber forming PZT gel containing 58.5 wt% PZT was synthesized by using zirconium-n-propylate, titanium-iso-propylate, lead acetate and butoxyethanol. Unseeded PZT gels and gels containing 0.5 wt% PZT perovskite seeds (Ø = 200–300 nm) could be extruded through a monofilament nozzle (Ø = 100 m) at pressures between 50 and 150 bar, whereas PZT gels, containing 1 and 2 wt% PZT particles, were pressed through the nozzle at higher pressures (200–300 bar). The microstructure of unseeded and seeded (0.5, 1, 2 wt% PZT) PZT fibers was characterized by SEM. Unseeded fibers had three different shells at 450°C: an external dense shell (approx. 200 nm thick), a middle shell consisting of a porous structure (1.5m thick) and the center of the fiber, characterized by a matrix containing globular particles. At 700°C, a 200–250 nm thick and dense external shell and a porous fiber interior were be observed. 2 wt% of PZT seeds was necessary to densify the fiber completely. The seeds were located in the center of each PZT perovskite rosette.     

Orientation control of perovskite thin films on glass substrates by the application of a seed layer prepared from oxide nanosheets

Orientation control of perovskite compounds was investigated by the application of a seed layer prepared from oxide nanosheets. An aqueous suspension of oxide nanosheets was prepared by the exfoliation of a layered compound of KCa₂Nb₃O₁₀ oxide grains. A seed layer composed of (TBA)Ca₂Nb₃O₁₀ nanosheets (TBA = tetrabutylammonium) was formed on a glass substrate by simply dip coating it in the suspension. Two kinds of perovskite compounds, LaNiO₃ (LNO) and Pb(Zr,Ti)O₃ (PZT) with a preferred orientation of (00l) were successfully grown on this seeded glass substrate. In this study, the relation between lattice mismatch and electrical properties is investigated. A large, oriented PZT film with a size of 5 ×4 cm shows an improved P-E hysteresis behavior by use of this orientation control.     

Synthesis and mechanism research of an ethylene glycol-based sol-gel method for preparing PZT nanopowders

Lead zirconate titanate nanopowders Pb(Zr_0.52Ti_0.48)O₃ (PZT) were prepared by modified sol-gel process in ethylene glycol system with zirconium nitrate as the zirconium source. The research showed that it was critical to add lead acetate after the reaction of zirconium nitrate and tetrabutyl titanate in ethylene glycol system for preparing PZT of exact titanium content. The reaction mechanisms of the sol synthesis, preparation of xerogel and agglutinating process were characterized through using FT-IR, NMR, TG-FTIR, and GC-MS. The experiment proved that ethylene glycol system did not rely on hydrolysis and condensation reactions in the process of the sol formation, but on the formation of chain or network large molecules from complexation of ethylene glycol and all Ti and minor Pd, Zr. In the preparation of xerogel, the complexation reaction was so completed that it formed large molecules network composed of metal and dioxyethyl. Bulk weight loss happened before 350°C in the process of sintering xerogel to prepare PZT nanopowders. Volatile matters and vapor phase decomposition resultants were primarily oxy-compounds including ethylene glycol, aldehyde-ketone compounds, carbon dioxide and nitrate radical conversion matters. After 350°C, primary vapor phase decomposition resultants were carbon dioxide and minor carbonyl compound.     

Polarization inscription in ferroelectric (111) PZT and (100) SBT films

Ferroelectric thin films form an equilibrium domain structure compatible with their respective crystallographic symmetry. In tetragonal (111) PZT, 90° domains prevail; in (pseudo-tetragonal) (100) SBT both 90° and 180° domains are present. The size of 90° domains has been measured for e.g., PZT as slabs of 15 nm width. Domain size is a result of stress minimization in the film during the paraelectric (PE) → ferroelectric (FE) transition. A precise and regular domain pattern for (111) PZT and (100) SBT films has been investigated in detail by TMSFM. Single domains can be addressed mechanically with the tip of an AFM. Such single domain switching corresponds to a data storage density of 200 Gbit/inch². Applications of ferroelectric and high- paraelectric materials for e.g., non-volatile data storage replacing DRAM devices or as sensors in infrared cameras are increasingly becoming popular.     

Microstructure and ferroelectric properties of r.f. magnetron sputtering derived PZT thin films deposited on interlayer (PbO/TiO2)

Lead zirconate titanate (PZT) thin films were deposited on Pt/Ti/SiO₂/Si and interlayer/Pt/Ti/SiO₂/Si substrate by radio frequency (r.f.) magnetron sputtering with a Pb_1.1Zr_0.53Ti_0.47O₃ target. The crystallization of the PZT thin films was formed only by substrate temperature. When interlayer (PbO/TiO₂) was inserted between the PZT thin film and the Pt electrode, the grain growth and processing temperature of the PZT thin films were considerably improved. Compared to PZT/Pt structure, the dielectric constant and polarization properties of the PZT/interlayer/Pt structure were fairly improved. In particular, PZT/interlayer/Pt at the substrate temperature of 400 °C showed prevalent ferroelectric properties (_r=475.97, tanδ=0.0591, P_r=23 μC/cm²). As a result of an X-ray photoelectron spectroscopy (XPS) depth-profile analysis, it was found that PZT/interlayer/Pt deposited only by substrate temperature without the post-annealing process via r.f. magnetron sputtering method remained independent of each other regardless of substrate temperatures.     

后退火温度对溅射沉积Pb(Zr0.52Ti0.48)O3铁电薄膜结构和性能的影响

在具有Ti缓冲层的Pt(111)底电极上,用射频溅射工艺在较低的衬底温度(370℃)和纯Ar气氛中沉积Pb(Zr0.52Ti0.48)O3(PZT)薄膜,沉积过程中基片架作15°摇摆以提高膜厚的均匀性。然后将样品在大气中进行5min快速热退火处理,退火温度550-680℃。用XRD、SEM分析薄膜的微结构,RT66A标准铁电测试系统测量样品的铁电和介电性能。结果表明,所沉积的Pt为(111)取向,仅当后退火温度高于580℃,沉积在Pt(111)上的PZT薄膜才能形成钙钛矿结构的铁电相,退火温度在580-600℃时结晶为(110)择优取向,退火温度高于600℃时结晶为(111)择优取向。PZT薄膜的极化强度随退火温度的升高而增加,但退火温度超过650℃时漏电流急剧上升,因此退火处理的温度对PZT薄膜的结构和性能有决定性的影响。     

Glycol-based sol-gel process for the fabrication of ferroelectric PZT thin films

A new sol-gel system using ethylene glycol was developed for the fabrication of PZT thin films with compositions near the morphotropic phase boundary Pb(Zr_0.52Ti_0.48)O₃. Ethylene glycol was used as both a chelating agent and a solvent to replace the highly toxic methoxyethanol used in previous formulations. Thin films were deposited by spin coating the solutions onto platinized silicon substrates. Films were completely crystallized by about 600°C and contained the ferroelectric perovskite phase. A dielectric constant of about 750–800 at 1 KHz was obtained for thin films of 0.3 µm thickness. The hysteresis measurements revealed a remanent polarization of 15 mC/cm² with a coercive field of 60 kV/cm.     

Micromechanical modelling of remanent properties of morphotropic PZT

The present paper investigates the capability of micromechanical material models to predict the ferroelectric behaviour of morphotropic PZT ceramics in a rate-independent approximation based on realistic microscopic material parameters. Starting point is a three-dimensional tetragonal model, which builds on the model of Pathak and McMeeking [2008. Three-dimensional finite element simulations of ferroelectric polycrystals under electrical and mechanical loading. Journal of the Mechanics and Physics of Solids 56, 663-683]. Volume fractions of the crystallographic variants represent the domain structure inside the grains. Interactions between the grains are taken into account by means of a representative volume element of the grain compound. A simplified set of realistic microscopic material parameters of the lattice in terms of Young's modulus, Poisson's ratio, dielectric constant, and spontaneous strain and polarisation is derived from experimental data and theoretical results given in the literature. The simulation of the macroscopic remanent polarisation and strain response due to two load cases shows explicitly that the tetragonal model is not capable to reproduce the behaviour of morphotropic PZT. Therefore, the model is extended by the rhombohedral phase, allowing a mixture of both phases with varying quantities inside the grains. A comparison of our results with experimental data shows a remarkably good agreement, revealing the capability of the extended model.     

PZT厚膜及高频超声换能器的研究

近年来,基于PZT厚膜的超声换能器研究受到了广泛的重视。本文综述了PZT厚膜制备技术的发展情况,简要介绍了水下声纳和医用超声领域中PZT厚膜型高频超声换能器的应用研制进展。