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

Optical properties of anatase TiO2 thin films prepared by aqueous sol–gel process at low temperature

Niobium pentoxide reacts actively with concentrate NaOH solution under hydrothermal conditions at as low as 120 degrees C. The reaction ruptures the corner-sharing of NbO7 decahedra and NbO6 octahedra in the reactant Nb2O5, yielding various niobates, and the structure and composition of the niobates depend on the reaction temperature and time. The morphological evolution of the solid products in the reaction at 180 degrees C is monitored via SEM: the fine Nb2O5 powder aggregates first to irregular bars, and then niobate fibers with an aspect ratio of hundreds form. The fibers are microporous molecular sieve with a monoclinic lattice, Na2Nb2O6 center dot(2)/3H2O. The fibers are a metastable intermediate of this reaction, and they completely convert to the final product NaNbO3 Cubes in the prolonged reaction of 1 h. This study demonstrates that by carefully optimizing the reaction condition, we can selectively fabricate niobate structures of high purity, including the delicate microporous fibers, through a direct reaction between concentrated NaOH solution and Nb2O5. This synthesis route is simple and suitable for the large-scale production of the fibers. The reaction first yields poorly crystallized niobates consisting of edge-sharing NbO6 octahedra, and then the microporous fibers crystallize and grow by assembling NbO6 octahedra or clusters of NbO6 octahedra and NaO6 units. Thus, the selection of the fibril or cubic product is achieved by control of reaction kinetics. Finally, niobates with different structures exhibit remarkable differences in light absorption and photoluminescence properties. Therefore, this study is of importance for developing new functional materials by the wet-chemistry process.

Structural evolution in a hydrothermal reaction between Nb2O5 and NaOH solution: from Nb2O5 grains to microporous Na2Nb2O6.2/3H2O fibers and NaNbO3 cubes.

Lead-free piezoelectric K0.5Na0.5NbO3 thin films for microelectromechanical systems were fabricated via chemical solution process using metal alkoxide. Perovskite K0.5Na0.5NbO3 (KNN) single-phase thin films with good leakage current properties were successfully prepared by optimizing the KxNaxNbO3 (x0.5) composition of the precursor solution. The KNN thin films prepared from the solution with K0.55Na0.55NbO3 composition showed typical ferroelectric P–E hysteresis and field-induced strain loops. The 2Pr and 2Ec values of the K0.55Na0.55NbO3 films were 14 µC/cm2 and 140 kV/cm, respectively. From the slope of the field-induced butterfly loop, the effective d33 was found to be 46 pm/V.

https://iopscience.iop.org/article/10.1143/JJAP.46.L311/pdf

Lead-Free Piezoelectric (K,Na)NbO3 Thin Films Derived from Metal Alkoxide Precursors

Over the past decade, the primary focus for improving the performance of nano-electronic metal interconnect structures has been to reduce the impact of resistance-capacitance (RC) delays via utilizing insulating dielectrics with ever lower values of dielectric permittivity. The integration and implementation of such low dielectric constant (i.e. low-k) materials has been fraught with numerous challenges. For intermetal and interlayer (ILD) low-k dielectrics, these challenges have been largely associated to integration with metal interconnect fabrication processes and well documented and reviewed in the literature. Although equally important, less attention has been given to other low-k dielectrics utilized in metal interconnect structures that are commonly referred to as low-k dielectric barriers (DB), etch stops (ES), and/or Cu capping layers (CCL). These materials present numerous challenges as well for integration into metal interconnect fabrication processes. However, they also have more stringent integrated functionality requirements relative to low-k ILD materials that serve only a basic purpose of electrically isolating adjacent metal lines. In this article, we review the integration challenges and associated integrated functionality requirements for low-k DB/ES/CCL materials with a focus on the current status and future direction needed for these materials to facilitate both Moore’s law (i.e. More Moore) and More than Moore scaling. © The Author(s) 2014. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any way and is properly cited. For permission for commercial reuse, please email: oa@electrochem.org. [DOI: 10.1149/2.0051501jss] All rights reserved.

https://iopscience.iop.org/article/10.1149/2.0051501jss/pdf

Dielectric Barrier, Etch Stop, and Metal Capping Materials for State of the Art and beyond Metal Interconnects

Deposition of SrTiO3 (STO) thin films by radio-frequency magnetron sputtering in an ultrahigh vacuum system at a low substrate temperature (∼200 °C) was performed in order to produce high-quality STO/p-Si (100) interfaces and STO insulator layers with dielectric constants of high magnitude. The STO films were identified as polycrystalline by x-ray diffraction, and were approximated with a layered structure according to the best fitting results of raw data from both Rutherford backscattering spectroscopy and variable angle spectroscopic ellipsometry. Room-temperature current–voltage and capacitance–voltage (C–V) measurements on Al/STO/p-Si diodes clearly revealed metal–insulator–semiconductor behavior, and the STO/p-Si interface state densities were of the order of 1011 eV−1 cm−2. The dielectric constant of the STO film was 65, and the dielectric loss factor varied between 0.05 and 0.55 for a frequency range of 1 kHz–10 MHz. For a 387 nm thick STO film, the dielectric breakdown field was 0.31 MV cm−1, and ...

Electrical properties of SrTiO3 thin films on Si deposited by magnetron sputtering at low temperature

The synthesis and mechanical properties of boron suboxide thin films deposited on silicon and graphite substrates was discussed. The deposition was performed using reactive magnetron sputtering tec ...

Synthesis and mechanical properties of boron suboxide thin films

Microstructure/dielectric property relationship of low temperature synthesised (Na,K)NbOx thin films

Low temperature growth and characterization of (Na,K)NbOx thin films

Deposition of SrTiO3 (STO) thin films by ultra-high vacuum rf magnetron sputtering was performed in order to produce high-quality STO/p-Si (1 0 0) interfaces and STO insulator layers with high diel 

Veronika Kugler

Papers

Electrical properties of SrTiO3 thin films on Si deposited by magnetron sputtering at low temperature

Synthesis and mechanical properties of boron suboxide thin films

Microstructure/dielectric property relationship of low temperature synthesised (Na,K)NbOx thin films

Low temperature growth and characterization of (Na,K)NbOx thin films

Electrical characterisation of SrTiO3/Si interfaces