We present a critical review that encompasses the fundamentals and state-of-the-art knowledge of barium titanate-based piezoelectrics. First, the essential crystallography, thermodynamic relations, and concepts necessary to understand piezoelectricity and ferroelectricity in barium titanate are discussed. Strategies to optimize piezoelectric properties through microstructure control and chemical modification are also introduced. Thereafter, we systematically review the synthesis, microstructure, and phase diagrams of barium titanate-based piezoelectrics and provide a detailed compilation of their functional and mechanical properties. The most salient materials treated include the (Ba,Ca)(Zr,Ti)O3, (Ba,Ca)(Sn,Ti)O3, and (Ba,Ca)(Hf,Ti)O3 solid solution systems. The technological relevance of barium titanate-based piezoelectrics is also discussed and some potential market indicators are outlined. Finally, perspectives on productive lines of future research and promising areas for the applications of these ma...

BaTiO3-based piezoelectrics: Fundamentals, current status, and perspectives

The temperature-composition phase diagram of barium calcium titanate zirconate (x(Ba0.7Ca0.3TiO3)-(1 − x)(BaZr0.2Ti0.8O3); BCTZ) has been reinvestigated using high-resolution synchrotron x-ray powder diffraction. Contrary to previous reports of an unusual rhombohedral-tetragonal phase transition in this system, we have observed an intermediate orthorhombic phase, isostructural to that present in the parent phase, BaTiO3, and we identify the previously assigned T-R transition as a T-O transition. We also observe the O-R transition coalescing with the previously observed triple point, forming a phase convergence region. The implication of the orthorhombic phase in reconciling the exceptional piezoelectric properties with the surrounding phase diagram is discussed.

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Revised structural phase diagram of (Ba0.7Ca0.3TiO3)-(BaZr0.2Ti0.8O3)

Developing eco-friendly high-performance piezoceramics without lead has become one of the most advanced frontiers in interdisciplinary research. Although potassium sodium-niobate {(K,Na)NbO3, KNN} based ceramics are believed to be one of the most promising lead-free candidates, the relatively inferior piezoelectric properties and strong temperature dependency have hindered their development for more than 50 years since being discovered in the 1950s. It was not until 2014 that our group initially proposed a new phase boundary (NPB) that simultaneously improved the piezoelectric properties and temperature stability of non-textured KNN-based ceramics to the level of partly lead-based ceramics. The NPB has been then proved by some researchers and believed to pave the way for "lead-free at last" proposed by E. Cross (Nature, 2004, 432, 24). However, the understanding of the NPB is still in its infancy, leaving many controversies, including the phase structure and physical mechanisms at the NPB as well as the essential difference when compared with other phase boundaries. In this context, we systematically summarized the origin and development of the NPB, focusing on the construction, structure and intrinsic trait of the NPB, the effects of the NPB on the performance, and the validity and related incipient devices of the NPB. Particularly, we concluded the phase structure and domain structure locating at the NPB, analyzed the physical mechanisms in depth, proposed the possible methods to further improve the performance at the NPB, and demonstrated the validity and scope of the NPB as well as the device application. Finally, we gave out our perspective on the challenges and future research of KNN-based ceramics with NPB. Therefore, we believe that this review could promote the understanding of the NPB and guide the future work of KNN-based ceramics.

/pdf/emerging-new-phase-boundary-in-potassium-sodium-niobate-2gjb40rkrw.pdf

Emerging new phase boundary in potassium sodium-niobate based ceramics

We investigate the dielectric, ferroelectric, and energy density properties of Pb-free (1 − x)BZT–xBCT ceramic capacitors at higher sintering temperature (1600 °C). A significant increase in the dielectric constant, with relatively low loss was observed for the investigated {Ba(Zr0.2Ti0.8)O3}(1−x){(Ba0.7Ca0.3)TiO3}x (x = 0.10, 0.15, 0.20) ceramics; however, electric breakdown was low (~140, 170, 134 kV/cm), and of which room temperature (300 K) charging curve energy density values are largest ~0.88, 0.94, and 0.87 J/cm3 with maximum high dielectric constant values ~7800, 8400, and 5200, respectively. Bulk ceramic BZT–BCT materials have shown interesting energy densities with good energy storage efficiency (~72 %) at high sintering temperature; they might be one of the strong candidates for high energy density capacitor applications in an environmentally protective atmosphere.

Structure, dielectric, ferroelectric, and energy density properties of (1 − x)BZT–xBCT ceramic capacitors for energy storage applications

In this paper, two displacive phase transitions around the morphotropic phase boundary (MPB) in Ba(Zr0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3 (BZT-xBCT) ceramics were detected by inspecting two anomalies of the Raman Ti4+-O2− longitudinal optical mode (∼725 cm−1). Further, permittivity and X-ray diffraction results demonstrated these two phase transitions originate from tetragonal (T) to rhombohedral (R) through an intermediate orthorhombic (O) phase. Importantly, we found that the maximum piezoelectric response (d33 = 545pC/N) was achieved at the boundary between the T and O phase, indicating that the giant piezoelectricity of BZT-xBCT may mainly stem from the T-O phase boundary due to easier polarization rotation and larger lattice softening.

Phase transitions and the piezoelectricity around morphotropic phase boundary in Ba(Zr0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3 lead-free solid solution

Ferroelectric lead-free thin films of 05(Ba07Ca03TiO3) – 05[Ba(Zr02Ti08)O3] (BCZT) were successfully deposited by pulsed laser deposition on Pt/TiO2/SiO2/Si substrates using a ceramic BCZT target prepared by conventional solid state reaction The in (111) direction orientated 600 nm thick films shows a clamped piezoelectric response of approximately d33,f = 80 pm/V and a dielectric coefficient of about ɛr = 1010; these are close to values obtained for lead zirconate titanate (PZT) films

M. Wuttig

Papers

Piezoelectric properties of 0.5(Ba0.7Ca0.3TiO3) – 0.5[Ba(Zr0.2Ti0.8)O3] ferroelectric lead-free laser deposited thin films