A large body of work has been reported in the last 5 years on the development of lead-free piezoceramics in the quest to replace lead–zirconate–titanate (PZT) as the main material for electromechanical devices such as actuators, sensors, and transducers. In specific but narrow application ranges the new materials appear adequate, but are not yet suited to replace PZT on a broader basis. In this paper, general guidelines for the development of lead-free piezoelectric ceramics are presented. Suitable chemical elements are selected first on the basis of cost and toxicity as well as ionic polarizability. Different crystal structures with these elements are then considered based on simple concepts, and a variety of phase diagrams are described with attractive morphotropic phase boundaries, yielding good piezoelectric properties. Finally, lessons from density functional theory are reviewed and used to adjust our understanding based on the simpler concepts. Equipped with these guidelines ranging from atom to phase diagram, the current development stage in lead-free piezoceramics is then critically assessed.

Perspective on the Development of Lead-free Piezoceramics

An overview of the state of art in ferroelectric thin films is presented. First, we review applications: microsystems' applications, applications in high frequency electronics, and memories based on ferroelectric materials. The second section deals with materials, structure (domains, in particular), and size effects. Properties of thin films that are important for applications are then addressed: polarization reversal and properties related to the reliability of ferroelectric memories, piezoelectric nonlinearity of ferroelectric films which is relevant to microsystems' applications, and permittivity and loss in ferroelectric films-important in all applications and essential in high frequency devices. In the context of properties we also discuss nanoscale probing of ferroelectrics. Finally, we comment on two important emerging topics: multiferroic materials and ferroelectric one-dimensional nanostructures. (c) 2006 American Institute of Physics.

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Ferroelectric thin films: Review of materials, properties, and applications

Potassium-sodium niobate lead-free piezoelectric materials: past, present, and future of phase boundaries.

Small, light weight and multifunctional electronic components are attracting much attention because of the rapid growth of the wireless communication systems and microwave products in the consumer electronic market. The component manufacturers are thus forced to search for new advanced integration, packaging and interconnection technologies. One solution is the low temperature cofired ceramic (LTCC) technology enabling fabrication of three-dimensional ceramic modules with low dielectric loss and embedded silver electrodes. During the past 15 years, a large number of new dielectric LTCCs for high frequency applications have been developed. About 1000 papers were published and ∼500 patents were filed in the area of LTCC and related technologies. However, the data of these several very useful materials are scattered. The main purpose of this review is to bring the data and science of these materials together, which will be of immense help to researchers and technologists all over the world. The comme...

Low loss dielectric materials for LTCC applications: a review

After twenty years of partly quiet and ten years of partly enthusiastic research into lead-free piezoceramics there are now clear prospects for transfer into applications in some areas. This mimics prior research into eliminating lead from other technologies that resulted in restricted lead use in batteries and dwindling use in other applications. A figure of merit analysis for key devices is presented and used to contrast lead-containing and lead-free piezoceramics. A number of existing applications emerge, where the usage of lead-free piezoceramics may be envisaged in the near future. A sufficient transition period to ensure reliability, however, is required. The use of lead-free piezoceramics for demanding applications with high reliability, displacements and frequency as well as a wide temperature range appears to remain in the distant future. New devices are outlined, where the figure of merit suggests skipping lead-containing piezoceramics altogether. Suggestions for the next pertinent research requirements are provided.

Transferring lead-free piezoelectric ceramics into application

Piezoelectric actuators convert electrical into mechanical energy and are implemented for many large-scale applications such as piezoinjectors and ink jet printers. The performance of these devices is governed by the electric-field-induced strain. Here, the authors describe the development of a class of lead-free (0.94−x)Bi0.5Na0.5TiO3–0.06BaTiO3–xK0.5Na0.5NbO3 ceramics. These can deliver a giant strain (0.45%) under both unipolar and bipolar field loadings, which is even higher than the strain obtained with established ferroelectric Pb(Zr,Ti)O3 ceramics and is comparable to strains obtained in Pb-based antiferroelectrics.

Giant strain in lead-free piezoceramics Bi0.5Na0.5TiO3–BaTiO3–K0.5Na0.5NbO3 system

Giant strain in lead-free piezoceramics Bi0.5Na0.5TiO3-BaTiO3-K0.5Na0.6NbO3 system

The mechanism of the giant unipolar strain recently observed in a lead-free piezoceramic, 0.92(Bi0.5Na0.5)TiO3-0.06BaTiO(3)-0.02(K0.5Na0.5)NbO3 [S.-T. Zhang, A. B. Kounga, E. Aulbach, H. Ehrenberg, and J. Rodel, Appl. Phys. Lett. 91, 112906 (2007) was investigated. The validity of the previously proposed mechanism that the high strain comes both from a significant volume change during the field-induced phase transition, from an antiferroelectric to a ferroelectric phase and the domain contribution from the induced ferroelectric phase was examined. Monitoring the volume changes from the simultaneously measured longitudinal and transverse strains on disk-shaped samples showed that the phase transition in this specific material does not involve any notable volume change, which indicates that there is little contribution from a volume change due to the phase transition to the total strain response. Temperature dependent hysteresis measurements on unpoled samples of a nearby ferroelectric composition, 0.93(Bi0.5Na0.5)TiO3-0.06BaTiO(3) -0.01(K0.5Na0.5)NbO3 demonstrated that the origin of the large strain is due to the presence of a nonpolar phase that brings the system back to its unpoled state once the applied electric field is removed, which leads to a large unipolar strain.

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Origin of the large strain response in (K0.5Na0.5)NbO3-modified (Bi0.5Na0.5)TiO3―BaTiO3 lead-free piezoceramics

Lead-free piezoelectric ceramics, 1� xyBi 0.5 Na 0.5 TiO 3 -xBaTiO 3 -yK 0.5 Na 0.5 NbO 3 0.05x 0.07 and 0.01y 0.03, have been synthesized by a conventional solid state sintering method. The room temperature ferroelectric and piezoelectric properties of these ceramics were studied. Based on the measured properties, the ceramics were categorized into two groups: group I compositions having dominant ferroelectric order and group II compositions displaying mixed ferroelectric and antiferroelectric properties at room temperature. A composition from group II near the boundary between these two groups exhibited a strain as large as 0.45% at an electric field of 8k V/ mm. Polarization in this composition was not stable in that the piezoelectric coefficient d33 at zero electric field was only about 30 pm/ V. The converse piezoelectric response becomes weaker when the composition deviated from the boundary between the groups toward either the ferroelectric or antiferroelectric compositions. These results were rationalized based on a field induced antiferroelectric-ferroelectric phase transition. © 2008 American Institute of Physics. DOI: 10.1063/1.2838472

http://scholarworks.unist.ac.kr/bitstream/201301/7442/1/2-s2.0-39349109251.pdf

Lead-free piezoceramics with giant strain in the system Bi0.5Na0.5TiO3–BaTiO3–K0.5Na0.5NbO3. I. Structure and room temperature properties

The temperature dependence of the dielectric and ferroelectric properties of lead-free piezoceramics of the composition (1−x−y)Bi0.5Na0.5TiO3–xBaTiO3–yK0.5Na0.5NbO3 (0.05⩽x⩽0.07, 0.01⩽y⩽0.03) was investigated. Measurements of the polarization and strain hystereses indicate a transition to predominantly antiferroelectric order when heating from room temperature to 150°C, while for 150<T<200°C both remnant polarization and coercive field increase. Frequency-dependent susceptibility measurements show that the transition is relaxorlike. For some samples, the transition temperature Td is high enough to allow mostly ferroelectric ordering at room temperature. These samples show a drastic increase of the usable strain under an external electric field just after the transition into the antiferroelectric state at high temperatures. For the other samples, Td is so low that they display significant antiferroelectric ordering already at room temperature. In these samples, the usable strain is relatively stable over a...

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Emil Aulbach

Papers

Giant strain in lead-free piezoceramics Bi0.5Na0.5TiO3–BaTiO3–K0.5Na0.5NbO3 system

Giant strain in lead-free piezoceramics Bi0.5Na0.5TiO3-BaTiO3-K0.5Na0.6NbO3 system

Origin of the large strain response in (K0.5Na0.5)NbO3-modified (Bi0.5Na0.5)TiO3―BaTiO3 lead-free piezoceramics

Lead-free piezoceramics with giant strain in the system Bi0.5Na0.5TiO3–BaTiO3–K0.5Na0.5NbO3. I. Structure and room temperature properties

Lead-free piezoceramics with giant strain in the system Bi0.5Na0.5TiO3–BaTiO3–K0.5Na0.5NbO3. II. Temperature dependent properties