Effect on Electrical Properties of Barium and Strontium Additions in the Lead Lanthanum Zirconate Stannate Titanate System

The effect of barium (Ba) and strontium (Sr) additions on the electrical properties of lead lanthanum zirconate stannate titanate (PLZST) ceramics and their electrically induced phase change behavior was examined. Sr additions decreased both the ferroelectric (FE) ↔ antiferroelectric (AFE) transition temperature ( T_AFE-FE ) and the temperature of the maximum dielectric constant ( T_MAX ). This indicates that Sr additions stabilize the AFE phase. Along with B-site modifications Sr additions can be used to decrease the switching field and hysteresis. Ba additions caused the temperature range of the AFE phase to narrow by increasing T_AFE-FE and decreasing T_MAX . This behavior indicates an ability to lower the switching field and suppress hysteresis. Using a combination of both A-site and B-site modifications it is possible to tailor the properties (for example, switching field, hysteresis, and operating temperature range) of this group of phase change materials to meet the requirements of specific applications.     

Low-Temperature Preparation of Nanocrystalline Lead Zirconate Titanate and Lead Lanthanum Zirconate Titanate Powders Using Triethanolamine

Nanocrystalline lead zirconate titanate (PZT) powders, with a Zr:Ti ratio of 60:40, have been prepared from a solution of triethanolamine (TEA) and Ti⁴⁺, Zr⁴⁺, and Pb²⁺ ions. The metal ions were in solution through complex formation with TEA. The soluble metal-ion–TEA complex formed the precursor material when it was completely dehydrated. Heat treatment of the precursor at 450°C resulted in single-phase PZT powders. The precursor and the heat-treated powders have been characterized by using thermal analysis and X-ray diffractometry (XRD) studies. The average particle size, as measured from X-ray line broadening and transmission electron microscopy studies, was ∼20 nm. PZT powders modified with 3 mol% of lanthanum (PLZT) also were prepared through this route and were investigated via XRD studies. The dielectric constants of the PZT and PLZT powders were 12475 and 11262, and their corresponding Curie temperatures were 362° and 315°C, respectively.     

Field-Forced Antiferroelectric-to-Ferroelectric Switching in Modified Lead Zirconate Titanate Stannate Ceramics

Electric-field-forced antiferroelectric-to-ferroelectric phase transitions in several compositions of modified lead zirconate titanate stannate antiferroelectric ceramics are studied for ultra-high-field-induced strain actuator applications. A maximum field-induced longitudinal strain of 0.85% and volume expansion of 0.95% are observed in the ceramic composition Pb_0.97La_0.02(Zr_0.66Ti_0.09Sn_0.25)O₃ at room temperature. Switching from the antiferroelectric form to the ferroelectric form is controlled by the nucleation of the ferroelectric phase from the antiferroelectric phase. A switching time of <1 μs is observed under the applied field above 30 kV/cm. The polarization and strains associated with the field-forced phase transition decrease with increasing switching cycle, a so-called fatigue effect. Two types of fatigue effects are observed in these ceramic compositions. In one, the fatigue effects only proceed to a limited extent and the properties may be restored by annealing above the Curie temperature, while in the other, the fatigue effects proceed to a large extent and the properties cannot be restored completely by heat treatment. Hydrostatic pressure increases the transition field and the switching time. But when the applied electric field is larger than the transition field, the induced polarization and strain are not sensitive to increasing hydrostatic pressure until the transition field approaches the applied field.     

Preparation and Properties of Lead Zirconate Stannate Titanate Sintered by Spark Plasma Sintering

Lanthanum-doped lead zirconate stannate titanate ceramics were successfully compacted to full density by spark plasma sintering (SPS). SPS samples densified at 900° or 950°C exhibit nearly full density and fine grain size (about 300 nm). Compared with samples from conventional sintering (CS), SPS samples show larger permittivity accompanied by a deterioration in dielectric loss and special strain hysteresis loops similar to those of ferroelectric relaxors, with a diffuse AFE–FE phase transition and less field-induced longitudinal strain. The differences in the properties of SPS and CS materials are attributed to the variations of the resultant microstructures, especially the grain size, of the ceramics.     

Fabrication and Electrical Properties of Lead Zirconate Titanate Thick Films

Thick films of lead zirconate titanate of the morphotropic phase boundary composition, Pb(Zr_0.52Ti_0.48)O₃, have been fabricated on platinum-buffered silicon using a modified sol–gel spin-coating technique. Crack-free films of 12-μm thickness can be uniformly deposited on 3-in.-diameter wafers with high yield and properties comparable to those of bulk ceramics. The thickness dependence of film structure and the dielectric, ferroelectric, and piezoelectric properties have been characterized over the thickness range of 1–12 μm. A strong (100) texture develops as film thickness increases above 5 μm; the films were marked by saturation values of longitudinal piezoelectric coefficient d ₃₃, 340 pC/N; remanent polarization, 27 μC/cm²; and dielectric permittivity, 1450. PZT films in this thickness range are extremely well-suited to application as electromechanical transduction media in silicon-based microelectromechanical systems (MEMS).     

Elastic-Plastic Contact Damage in a Lead Lanthanum Zirconate Titanate

Spherical indenters were used to produce elastic-plastic contact damage in a lead lanthanum zirconate titanate (PLZT) under conditions of quasi-static and impact loading. The extent of radial cracking produced under both loading conditions showed good correlation with the response predicted by an earlier fracture mechanics analysis for quasi-static conditions. Calculated radial crack lengths corresponding to conditions of impact loading exhibited excellent agreement with experimentally measured values. The dynamic hardness of the PLZT was determined to be ∼ 1.5 times the quasi-static hardness. Differences in the radial crack lengths produced under the two loading conditions were attributed primarily to this difference in hardness response.     

Fabrication and Electrical Properties of Lead Zirconate Titanate Thick Films on Si Substrate by Using Lanthanum Nickelate Buffer Layer

Lead zirconate titanate PbZr_0.53Ti_0.47O₃ (PZT) thick films have been deposited on silicon substrate by modified metallorganic decomposition process. Crack-free PZT films of 8 μm thickness can be obtained by using lanthanum nickelate LaNiO₃ (LNO) as buffer layer. The greater LNO thickness, the greater thickness of crack-free PZT can be obtained. The X-ray diffraction measurements show the films exhibit a single perovskite phase with (110) preferred orientation. SEM measurements showed the PZT thick films have a columnar structure with grain size about 60–200 nm. The thickness dependence of ferroelectric, dielectric, and piezoelectric properties of PZT thick films have been characterized over the thickness range of 1–8 μm. For PZT with thickness of 8 μm, P _r and E _c are 30 μC/cm² and 35 kV/cm, and dielectric constant and dielectric loss are 1030 and 0.031, respectively. The piezoelectric coefficient ( d ₃₃) of PZT with 8 μm thickness is obtained to be 77 pm/V. PZT thick films on LNO-coated Si substrate are potential for MEMS applications.     

Synthesis of Lead Zirconate Titanate Stannate Antiferroelectric Thick Films by Sol-Gel Processing

The effects of different sintering procedures on the preparation of antiferroelectric thick films and the structure–property relations in these films were studied. An acetic acid-based sol–gel processing with multistep annealing and suitable lead oxide overcoat layers was developed to fabricate both niobium-doped and lanthanum-doped lead zirconate titanate stannate antiferroelectric thick films. The 5-μm-thick Pb_0.99Nb_0.02(Zr_0.85Sn_0.13Ti_0.02)_0.98O₃ films demonstrate typical square hysteresis loops with a maximum polarization of 40 μC/cm², zero remanent polarization, an antiferroelectric-to-ferroelectric phase transition field of 153 kV/cm, and a ferroelectric-to-antiferroelectric phase transition field of 97 kV/cm. The dielectric constant and dielectric loss are 283 and 1.7%, respectively. The 5-μm-thick Pb_0.97La_0.02(Zr_0.65Sn_0.31Ti_0.04)O₃ films display typical slanted hysteresis loops with very small hysteresis, a maximum polarization of 35.0 μC/cm², and zero remanent polarization. The dielectric constant and dielectric loss are 434 and 2.0%, respectively.     

组成对锆钛酸铅铁电薄膜电性能影响的研究进展

锆钛酸铅材料因具有优异的介电、压电和铁电性被广泛用于制作电容器、压电器件和铁电随机存储器等功能器件.本文综述了锆钛酸铅铁电薄膜材料中锆钛比、掺杂种类及掺量对其介电性和铁电性的影响,并提出了亟待解决的问题.     

Effect of Manganese Ion Diffusion on the Microstructural Evolution of Lead Lanthanum Zirconate Titanate Ceramic

Microstructural evolution of lead lanthanum zirconate titanate (PLZT) ceramics caused by diffusion of the Mn ion was observed. Specimens with layered structures were fabricated by copressing a PLZT powder (9/65/35) doped with Mn and same PLZT powder without the dopant. When the copressed specimen was sintered at 1200°C in air, the Mn ion diffused out of the doped region. The region originally containing the Mn ions was totally free of pores while all other regions remained porous. The formation of lattice vacancies, as a result of Mn diffusion, was attributed to the enhanced material transport and the resultant rapid densification.     

Ferroelastic Properties of Lead Zirconate Titanate Ceramics

To increase the reliability of multilayer actuators, calculation of the mechanical stress inside the device during operation is important. This paper shows that the small-signal value of the elastic constant s is not sufficient to describe the complicated behavior of lead zirconate titanate (PZT) ceramics. Therefore, compressive strain and depolarization have been measured as a function of large-signal stress applied parallel to the poling direction. The nonlinear dependence of the strain and depolarization can clearly be explained by domain processes. Soft and hard PZT ceramics have been investigated. In hard PZT, domain switching appears at higher stresses than in soft PZT. Moreover, in hard PZT, the domains partly switch back during unloading. The critical stress (coercive stress) necessary for a domain-switching process shows a dependence on the Zr:Ti ratio that is quite similar to the dependence of the electric coercive field. The influence of an electric field applied parallel to the poling direction and superimposed on the compression experiment also has been examined. The coercive stress depends linearly on the electric field. The linear coefficient of this relation is given by the ratio of depolarization to compressive strain caused by domain switching.     

助熔剂法生长的锆钛锡酸铅镧(PLZST)晶体及生长余料的组分分析

以PbO-PbF2复合体作为助熔剂,采有助熔剂自发成核缓冷法率先制备出成分为（Pb0.94La0.04)(Zr0.37Ti0.18Sn0.45)O3的驰豫型复合钙钛矿结构锆钛锡酸铅镧（PLZST）晶体,合适的生长工艺为：助熔剂中PbO与PbF2的摩尔比为0.55:0.45,原料与助熔剂的摩尔比为1：1,保温温度1250℃,保温时间12h,快降温速率为50－100℃／h,慢降温速率为1－5℃/h,快速降温与慢速降温的转变温度为1150℃,本工作对晶体及晶体生长余料中的组分进行了分析,结果表明：对一定组成的初始配料,PLZST晶体组成相对富La,Ti和Zr,生长后的余料相对富Sn,PLZST晶体中存在两种包裹体缺陷,晶体除包裹体以外各元素分布均匀,生长余料中各元素分布较均匀,存在某些元素的相对富集区域。     

Electric Fatigue in Ferroelectric Lead Zirconate Stannate Titanate Ceramics Prepared by Spark Plasma Sintering

Ferroelectric lead zirconate stannate titanate ceramics were prepared by spark plasma sintering (SPS). Compared with its counterpart densified by conventional sintering (CS), the SPS material shows a smaller remanent polarization and maximum strain as well as a higher coercive field. Electric fatigue in both materials was investigated. In contrast to CS samples, the SPS specimens show a lower resistance to bipolar electric cycling, characterized by a faster decrease in remanent polarization and maximum strain at cycle number below 10^6.5 and a subsequent slower reduction of the properties at high cycle numbers up to 10⁸.     

Electric Fatigue in Antiferroelectric Lead Zirconate Stannate Titanate Ceramics Prepared by Spark Plasma Sintering

The fatigue behavior of lead zirconate stannate titanate (PZST) ceramics prepared by spark plasma sintering (SPS) was investigated. Polarization and strain hysteresis loops were monitored. The material shows a high resistance to fatigue because of bipolar electric cycling. Both maximum strain and switchable polarization first show a fatigue stage 0 to 10⁵ cycles and then a fatigue-free period up to 10⁸ cycles. The maximum losses of maximum strain and switchable polarization are 18% and 10% of their initial values, respectively. The dominant fatigue mechanism is assigned to the pinning of domain walls by charged defects.     

Bistable Optical Information Storage Using Antiferroelectric-Phase Lead Lanthanum Zirconate Titanate Ceramics

A recently discovered photostorage effect in antiferroelectric-phase (AFE-phase) lead lanthanum zirconate titanate (PLZT) compositions appears to be particularly applicable to binary optical information storage. The basis for bistable optical information storage is that exposure to near-UV or visible light shifts the electric field threshold of the phase transition between the field-induced ferroelectric (FE) phase and the stable AFE phase in the direction of the initial AFE → FE phase transition. Properties of this photoactivated shift of the FE → AFE phase transition, including preliminary photosensitivity measurements and photostorage mechanisms, are presented. Photosensitivity enhancement by ion implantation is also discussed.     

热压烧结对锆钛酸铅镧陶瓷电卡效应的影响

探讨热压烧结工艺对PLZT(锆钛酸铅镧)陶瓷材料介电击穿性能、饱和极化强度以及电卡性能的影响。通过X射线衍射和扫描电子显微镜,分析陶瓷样品的相组成和微观结构。结果表明,热压烧结法有助于控制陶瓷晶粒的生长,提高陶瓷的致密度并增大陶瓷的介电击穿场强,从而有效提高陶瓷的电卡性能以及电卡转换效率。在328 K(55℃)与478 K(205℃)附近,分别发生低温铁电三方相到高温铁电三方相的相变(FRL-FRH)以及高温铁电三方相到立方顺电相(FRH-Pc)的相变,展现了比较好的弛豫性,在室温下达到3.6 K的绝热温变与1.8×0-7(K·m)/V的电卡转换效率,具有良好的电卡性能。     

Polarization Switching of and Electron Emission from Lead Lanthanum Zirconate Titanate Ceramics

This paper focuses on understanding the influence of ma-terial properties on the complicated ferroelectric (FE) emis-sion process. Three different compositions in the lead lan-thanum zirconate titanate (PLZT) system were chosen for study, based on their widely different dielectric and ferro-electric properties: antiferroelectric (AFE) 2/95/5, nor-mal ferroelectric 8/65/35, and nonferroelectric 15/65/35. Repeatable emission was obtained from the 2/95/5 compo-sition, which could also be modulated at high frequency (200 kHz). The fast AFE ⇆ FE phase transition is respon-sible for the FE emission properties of this material, which is supported by the relationship between the switching cur-rent and the emission current. Comparatively, FE emission from the 8/65/35 composition degraded rapidly, which was attributed to decreases in the remanent polarization. No emission signal was detected from the 15/65/35 composi-tion, because no switching activity occurs, which can be interpreted as additional evidence that electron emission from the previously mentioned two compositions was in-deed a FE emission process.     

Effect of Lead Zirconate Titanate Seeds on PtxPb Formation during the Pyrolysis of Lead Zirconate Titanate Thin Films

Lead zirconate titanate (PZT) thin films were prepared on platinized silicon substrates by dip-coating using a modified diol-based sol–gel route without and with up to 5 mol% PZT nanometric seeds dispersed in the precursor sol. A metastable intermetallic Pt _x Pb phase formed at the early stages of heat treatment. XRD, TEM, and RBS revealed that the thickness and stoichiometry of the Pt _x Pb layer varied with the concentration of seeds and heat treatment of the films. The relation of the Pt _x Pb layer to the final crystalline texture of the PZT thin films is reported and discussed.     

Properties of Lead Zirconate Titanate Thick-Film Piezoelectric Actuators on Ceramic Substrates

Lead zirconate titanate (PZT) is a piezoelectric material that can sense or respond to mechanical deformations and can be used in ceramic electro-mechanical systems (C-MEMS). The microstructural, electrical, and piezoelectric characteristics of thick PZT films on low-temperature cofired ceramics (LTCC) and alumina substrates were studied. The PZT composition was prepared with low-melting-point additives in order to decrease the sintering temperature and to be compatible with thick-film technology. The integration of the PZT thick-film materials on ceramic substrates could lead to degradation of the PZT's characteristics due to the interactions between an active PZT layer and a substrate, particularly with glassy LTCC material. To minimize the interactions with LTCC substrates, an intermediate PZT barrier layer was integrated. The value of the piezoelectric coefficient d ₃₃ was found to be up to 120 pC/N on an alumina substrate and approximately 50 on an LTCC substrate. Based on these results, a cantilever-type actuator was designed and fabricated on alumina substrates. Under an applied voltage of 200 V, the maximum tip deflection was about 5 μm.     

Effect of the Magnetostrictive Layer on Magnetoelectric Properties in Lead Zirconate Titanate/Terfenol-D Laminate Composites

Magnetoelectric laminate composites of piezoelectric/magnetostrictive materials were prepared by stacking and bonding together a PZT disk and two layers of Terfenol-D disks with different directions of magnetostriction. These composites were studied to investigate (i) dependence on the magnetostriction direction of the Terfenol-D disk and (ii) dependence on the direction of the applied ac magnetic field. Three different types of assemblies were prepared by using two types of disks: one with magnetostriction along the radial direction, the other with magnetostriction along the thickness direction. The maximum magnetoelectric voltage coefficient (d E /d H ) of 5.90 V/cm·Oe was obtained for a design where the composite was made by two Terfenol-D layers with a radial magnetostriction direction.