Recent development in lead-free perovskite piezoelectric bulk materials

Dielectric capacitors with ultrahigh power densities are fundamental energy storage components in electrical and electronic systems. However, a long-standing challenge is improving their energy densities. We report dielectrics with ultrahigh energy densities designed with polymorphic nanodomains. Guided by phase-field simulations, we conceived and synthesized lead-free BiFeO3-BaTiO3-SrTiO3 solid-solution films to realize the coexistence of rhombohedral and tetragonal nanodomains embedded in a cubic matrix. We obtained minimized hysteresis while maintaining high polarization and achieved a high energy density of 112 joules per cubic centimeter with a high energy efficiency of ~80%. This approach should be generalizable for designing high-performance dielectrics and other functional materials that benefit from nanoscale domain structure manipulation.

Ultrahigh–energy density lead-free dielectric films via polymorphic nanodomain design

A superior piezoelectric coefficient (d33 = 570 ± 10 pC N"1 ), the highest value reported to date in potassium-sodium niobate-based ceramics, is obtained in (1-x-y)K1-w Naw Nb1-z Sbz O3-y BaZrO3-x - Bi0.5 K0.5 HfO3 ceramics. This high d33 value can be ascribed to the co-existence of "nano-scale strain domains" (1-2 nm) and a high density of ferroelectric domain boundaries. Therefore, ternary KNN-based ceramics demonstrate the potential for applications.

Superior Piezoelectric Properties in Potassium-Sodium Niobate Lead-Free Ceramics.

Multiferroic bismuth ferrite-based materials for multifunctional applications: Ceramic bulks, thin films and nanostructures

Lead-based piezoelectric materials are currently facing global restrictions due to their lead toxicity. Thus it is urgent to develop lead-free substitutes with high piezoelectricity and temperature stability, among which, potassium-sodium niobate [(K,Na)NbO3, KNN] has the most potential. It is very difficult to simultaneously achieve high piezoelectric performance and reliable stability in KNN-based systems. In particular, the structural/physical origin for their high piezoelectricity is still unclear, which hinders property optimization. Here we report the achievement of high temperature stability (less than 10% variation for electric field-induced strain from 27 °C to 80 °C), good fatigue properties (stable up to 106 cycles) as well as an enhanced piezoelectric coefficient (d33) of 525 pC N−1 in (1 − x)(K1−yNay)(Nb1−zSbz)O3–xBi0.5(Na1−wKw)0.5HfO3 (KNNS–BNKH) ceramics through manipulating the rhombohedral–tetragonal (R–T) phase boundary. The structural origin of their high piezoelectric performance can be attributed to a hierarchical nanodomain architecture, where the local structure inside nanodomains comprises R and T nanotwins. The physical origin can be attributed to low domain wall energy and nearly vanishing polarization anisotropy, facilitating easy polarization rotation among different states. We believe that the new breakthrough will open a window for the practical applications of KNN-based ceramics.

The structural origin of enhanced piezoelectric performance and stability in lead free ceramics

A bismuth ferrite and barium titanate solid solution compound can achieve good piezoelectric properties with a high Curie temperature when fabricated with low-temperature sintering followed by a water-quenching process, with no complicated grain alignment processes performed. By adding the super-tetragonal bismuth gallium oxide to the compound, the piezoelectric properties are as good as those of lead zirconate titanate ceramics.

High-Performance Lead-Free Piezoceramics with High Curie Temperatures

The crystal structures and electrical properties of lead-free BiFeO3-BaTiO3 [(1-x)BFxBT] piezoelectric system are investigated as a function of BaTiO3 concentration. The well-saturated P-E hysteresis loop was observed in the 0.80BiFeO3–0.20BaTiO3 composition system, while a less hysteretic strain-electric field curve was exhibited by the 0.70BiFeO3–0.30BaTiO3 with a strain hysteresis of 16%, the value comparable to PZT-based piezoelectric ceramics. The crystal structures investigated under the synchrotron radiation X-ray diffraction exhibited a rhombohedral structure for BFBT system with x = 0.10–0.25 and a pseudo-cubic structure for BFBT system with x = 0.30–0.40. The structural phase diagram for the BiFeO3-BaTiO3 system is suggested based on the results of temperature-dependent synchrotron radiation X-ray diffraction measurement and investigated electrical properties.

Structural and electrical characteristics of potential candidate lead-free BiFeO3-BaTiO3 piezoelectric ceramics

The structure of lead-free (1-x)(Bi0.5Na0.5)TiO3-xSrTiO3 (BNT-STx) ceramics was analyzed by the Rietveld method, using X-ray diffraction and neutron scattering data. The structural refinement results suggest that the crystal structure successively changes with SrTiO3 concentration, x, from the rhombohedral phase (x = 0.00) to rhombohedral and tetragonal (x = 0.10–0.30), tetragonal and cubic (x = 0.40–0.60), and finally cubic (x = 0.80–1.00) phases. Correlation between the charge sensor constant (d33) and the weighted off-center value (dw) was observed, which may be attributed to the increased dipole motion in the unit cell due to an increased tendency to respond to external stimulation. Furthermore, an improved charge sensor constant (d33) of 140 pC/N was observed for BNT-ST0.20, and a large strain of 0.25% and a d33* value of 443 pm/V were observed from x = 0.30.

A correlation between piezoelectric response and crystallographic structural parameter observed in lead-free (1-x)(Bi0.5Na0.5)TiO3–xSrTiO3 piezoelectrics

Electrical properties and phase of BaTiO3–SrTiO3 solid solution

The structural and electrical properties of the virgin, annealed, and quenched samples of 0.80BiFeO3–0.20BaTiO3 lead-free ceramics were investigated. The crystal structures investigated with the structure refinement method exhibited a rhombohedral structure for all the samples. The significant enhancement of ferroelectric and piezoelectric properties is ascribed to the relaxation of the lattice strain induced in the samples after the heat treatment. The bond-length calculated from the final structure refinement results revealed the increment of the A-O bond-length after the heat treatment, while the B-O bond-length was maintained in all the virgin, annealed, and quenched samples suggesting the specific influence of the lattice strain at the A-site of the material system.

Sangwook Kim

Papers

High-Performance Lead-Free Piezoceramics with High Curie Temperatures

Structural and electrical characteristics of potential candidate lead-free BiFeO3-BaTiO3 piezoelectric ceramics

A correlation between piezoelectric response and crystallographic structural parameter observed in lead-free (1-x)(Bi0.5Na0.5)TiO3–xSrTiO3 piezoelectrics

Electrical properties and phase of BaTiO3–SrTiO3 solid solution

Revealing the role of heat treatment in enhancement of electrical properties of lead-free piezoelectric ceramics