Abstract Piezoelectric materials enable the conversion of mechanical energy into electrical energy and vice‐versa. Ultrahigh piezoelectricity has been only observed in single crystals. Realization of piezoelectric ceramics with longitudinal piezoelectric constant (d33) close to 2000 pC N–1, which combines single crystal‐like high properties and ceramic‐like cost effectiveness, large‐scale manufacturing, and machinability will be a milestone in advancement of piezoelectric ceramic materials. Here, guided by phenomenological models and phase‐field simulations that provide conditions for flattening the energy landscape of polarization, a synergistic design strategy is demonstrated that exploits compositionally driven local structural heterogeneity and microstructural grain orientation/texturing to provide record piezoelectricity in ceramics. This strategy is demonstrated on [001]PC‐textured and Eu3+‐doped Pb(Mg1/3Nb2/3)O3‐PbTiO3(PMN‐PT) ceramics that exhibit the highest piezoelectric coefficient (small‐signald33of up to 1950 pC N–1and large‐signald33* of ≈2100 pm V–1) among all the reported piezoelectric ceramics. Extensive characterization conducted using high‐resolution microscopy and diffraction techniques in conjunction with the computational models reveals the underlying mechanisms governing the piezoelectric performance. Further, the impact of losses on the electromechanical coupling is identified, which plays major role in suppressing the percentage of piezoelectricity enhancement, and the fundamental understanding of loss in this study sheds light on further enhancement of piezoelectricity. These results on cost‐effective and record performance piezoelectric ceramics will launch a new generation of piezoelectric applications.
more »
« less
Enhanced Piezoelectric, Ferroelectric, and Electrostrictive Properties of Lead‐Free (1‐ x )BCZT‐( x )BCST Electroceramics with Energy Harvesting Capability
Abstract Next‐generation electronics and energy technologies can now be developed as a result of the design, discovery, and development of novel, environmental friendly lead (Pb)‐free ferroelectric materials with improved characteristics and performance. However, there have only been a few reports of such complex materials’ design with multi‐phase interfacial chemistry, which can facilitate enhanced properties and performance. In this context, herein, novel lead‐free piezoelectric materials (1‐x)Ba0.95Ca0.05Ti0.95Zr0.05O3‐(x)Ba0.95Ca0.05Ti0.95Sn0.05O3, are reported, which are represented as (1‐x)BCZT‐(x)BCST, with demonstrated excellent properties and energy harvesting performance. The (1‐x)BCZT‐(x)BCST materials are synthesized by high‐temperature solid‐state ceramic reaction method by varyingxin the full range (x= 0.00–1.00). In‐depth exploration research is performed on the structural, dielectric, ferroelectric, and electro‐mechanical properties of (1‐x)BCZT‐(x)BCST ceramics. The formation of perovskite structure for all ceramics without the presence of any impurity phases is confirmed by X‐ray diffraction (XRD) analyses, which also reveals that the Ca2+, Zr4+, and Sn4+are well dispersed within the BaTiO3lattice. For all (1‐x)BCZT‐(x)BCST ceramics, thorough investigation of phase formation and phase‐stability using XRD, Rietveld refinement, Raman spectroscopy, high‐resolution transmission electron microscopy (HRTEM), and temperature‐dependent dielectric measurements provide conclusive evidence for the coexistence of orthorhombic + tetragonal (Amm2+P4mm) phases at room temperature. The steady transition ofAmm2crystal symmetry toP4mmcrystal symmetry with increasingxcontent is also demonstrated by Rietveld refinement data and related analyses. The phase transition temperatures, rhombohedral‐orthorhombic (TR‐O), orthorhombic‐ tetragonal (TO‐T), and tetragonal‐cubic (TC), gradually shift toward lower temperature with increasingxcontent. For (1‐x)BCZT‐(x)BCST ceramics, significantly improved dielectric and ferroelectric properties are observed, including relatively high dielectric constantεr≈ 1900–3300 (near room temperature),εr≈ 8800–12 900 (near Curie temperature), dielectric loss, tanδ≈ 0.01–0.02, remanent polarizationPr≈ 9.4–14 µC cm−2, coercive electric fieldEc≈ 2.5–3.6 kV cm−1. Further, high electric field‐induced strainS≈ 0.12–0.175%, piezoelectric charge coefficientd33≈ 296–360 pC N−1, converse piezoelectric coefficient ≈ 240–340 pm V−1, planar electromechanical coupling coefficientkp≈ 0.34–0.45, and electrostrictive coefficient (Q33)avg≈ 0.026–0.038 m4C−2are attained. Output performance with respect to mechanical energy demonstrates that the (0.6)BCZT‐(0.4)BCST composition (x= 0.4) displays better efficiency for generating electrical energy and, thus, the synthesized lead‐free piezoelectric (1‐x)BCZT‐(x)BCST samples are suitable for energy harvesting applications. The results and analyses point to the outcome that the (1‐x)BCZT‐(x)BCST ceramics as a potentially strong contender within the family of Pb‐free piezoelectric materials for future electronics and energy harvesting device technologies.
more »
« less
- Award ID(s):
- 1827745
- PAR ID:
- 10414549
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Small
- ISSN:
- 1613-6810
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract The hafnate perovskites PbHfO3(antiferroelectric) and SrHfO3(“potential” ferroelectric) are studied as epitaxial thin films on SrTiO3(001) substrates with the added opportunity of observing a morphotropic phase boundary (MPB) in the Pb1−xSrxHfO3system. The resulting (240)‐oriented PbHfO3(Pba2) films exhibited antiferroelectric switching with a saturation polarization ≈53 µC cm−2at 1.6 MV cm−1, weak‐field dielectric constant ≈186 at 298 K, and an antiferroelectric‐to‐paraelectric phase transition at ≈518 K. (002)‐oriented SrHfO3films exhibited neither ferroelectric behavior nor evidence of a polarP4mmphase . Instead, the SrHfO3films exhibited a weak‐field dielectric constant ≈25 at 298 K and no signs of a structural transition to a polar phase as a function of temperature (77–623 K) and electric field (–3 to 3 MV cm−1). While the lack of ferroelectric order in SrHfO3removes the potential for MPB, structural and property evolution of the Pb1−xSrxHfO3(0 ≤x < 1) system is explored. Strontium alloying increased the electric‐breakdown strength (EB) and decreased hysteresis loss, thus enhancing the capacitive energy storage density (Ur) and efficiency (η). The composition, Pb0.5Sr0.5HfO3produced the best combination ofEB = 5.12 ± 0.5 MV cm−1,Ur = 77 ± 5 J cm−3, and η = 97 ± 2%, well out‐performing PbHfO3and other antiferroelectric oxides.more » « less
-
Abstract We report on structural, microstructural, spectroscopic, dielectric, electrical, ferroelectric, ferromagnetic, and magnetodielectric coupling studies of BiFeO3–GdMnO3[(BFO)1–x–(GMO)x], wherexis the concentration of GdMnO3(x= 0.0, 0.025, 0.05, 0.075, 0.1, 0.15, and 0.2), nanocrystalline ceramic solid solutions by auto-combustion method. The analysis of structural property by Rietveld refinement shows the existence of morphotropic phase boundary (MPB) atx= 0.10, which is in agreement with the Raman spectroscopy and high resolution transmission electron microscopy (HRTEM) studies. The average crystallite size obtained from the transmission electron microscopy (TEM) and x-ray line profile analysis was found to be 20–30 nm. The scanning electron micrographs show the uniform distribution of grains throughout the surface of the sample. The dielectric dispersion behavior fits very well with the Maxwell-Wagner model. The frequency dependent phase angle (θ) study shows the resistive nature of solid solutions at low frequency, whereas it shows capacitive behavior at higher frequencies. The temperature variation of dielectric permittivity shows dielectric anomaly at the magnetic phase transition temperature and shifting of the phase transition towards the lower temperature with increasing GMO concentration. The Nyquist plot showed the conduction mechanism is mostly dominated by grains and grain boundary resistances. The ac conductivity of all the samples follows the modified Jonscher model. The impedance and modulus spectroscopy show a non-Debye type relaxation mechanism which can be modeled using a constant phase element (CPE) in the equivalent circuit. The solid-solutions of BFO-GMO show enhanced ferromagnetic-like behavior at room temperature. The ferroelectric polarization measurement shows lossy ferroelectric behavior. The frequency dependent magnetocapacitance and magnetoimpedance clearly show the existence of intrinsic magnetodielectric coupling. The (BFO)1–x–(GMO)xsolid solutions withx= 0.025–0.075 show significantly higher magnetocapacitance and magnetoimpedance compared to the pure BFO.more » « less
-
Abstract The availability of materials with high electrocaloric (EC) strengths is critical to enabling EC refrigeration in practical applications. Although large EC entropy changes, ΔSEC, and temperature changes, ΔTEC, have been achieved in traditional thin‐film ceramics and polymer ferroelectrics, they require the application of very high electric fields and thus their EC strengths ΔSEC/ΔEand ΔTEC/ΔEare too low for practical applications. Here, a fundamental thermodynamic description is developed, and extraordinarily large EC strengths of a metal‐free perovskite ferroelectric [MDABCO](NH4)I3(MDABCO) are predicted. The predicted EC strengths: isothermal ΔSEC/ΔEand adiabatic ΔTEC/ΔEfor MDABCO are 18 J m kg−1K−1MV−1and 8.06 K m MV−1, respectively, more than three times the largest reported values in BaTiO3single crystals. These predictions strongly suggest the metal‐free ferroelectric family of materials as the best candidates among existing materials for EC applications. The present work not only presents a general approach to developing thermodynamic potential energy functions for ferroelectric materials but also suggests a family of candidate materials with potentially extremely high EC performance.more » « less
-
Iron-chalcogenide superconductors FeSe1−xSxpossess unique electronic properties such as nonmagnetic nematic order and its quantum critical point. The nature of superconductivity with such nematicity is important for understanding the mechanism of unconventional superconductivity. A recent theory suggested the possible emergence of a fundamentally new class of superconductivity with the so-called Bogoliubov Fermi surfaces (BFSs) in this system. However, such an ultranodal pair state requires broken time-reversal symmetry (TRS) in the superconducting state, which has not been observed experimentally. Here, we report muon spin relaxation (μSR) measurements in FeSe1−xSxsuperconductors for0≤x≤0.22covering both orthorhombic (nematic) and tetragonal phases. We find that the zero-field muon relaxation rate is enhanced below the superconducting transition temperatureTcfor all compositions, indicating that the superconducting state breaks TRS both in the nematic and tetragonal phases. Moreover, the transverse-fieldμSR measurements reveal that the superfluid density shows an unexpected and substantial reduction in the tetragonal phase (x>0.17). This implies that a significant fraction of electrons remain unpaired in the zero-temperature limit, which cannot be explained by the known unconventional superconducting states with point or line nodes. The TRS breaking and the suppressed superfluid density in the tetragonal phase, together with the reported enhanced zero-energy excitations, are consistent with the ultranodal pair state with BFSs. The present results reveal two different superconducting states with broken TRS separated by the nematic critical point in FeSe1−xSx, which calls for the theory of microscopic origins that account for the relation between nematicity and superconductivity.more » « less
An official website of the United States government
