22 Search Results

Antiferroelectrics are fundamental mother compounds critical in developing innovative lead-free piezoelectrics and ferroelectrics and hold great promise for wide-ranging applications in energy conversion and electronic devices. However, harnessing their superior properties presents a significant challenge due to the delicate balance required between their various states. Here, in this study, through the unique design of nanopillar structures to alleviate the local polar heterogeneity, we have achieved significantly improved piezo-/ferro-electricity in classic lead-free antiferroelectric Ag_xNbO_3-δ (x = 1, 0.9, and 0.8) epitaxial thin films. The effective piezoelectric coefficient reaches 440 pm V^–1, 1 order of magnitude larger than the stoichiometric AgNbO₃, rivalingmore » classic lead zirconate titanate piezoelectrics. Atomic-scale electron microscopy investigations unravel the underlying mechanisms. The nanopillars, characterized by antisite occupancy of both Ag and Nb atoms and forming out-of-phase boundaries with the matrix, reduce the local crystal symmetry via interphase strain. This leads to the creation of flexible multinanodomain structures that significantly facilitate polarization rotation, thus substantially enhancing the piezoelectric performance. This study demonstrates the feasibility of engineering local heterogeneity through nanopillar design, offering a generally applicable method for property improvement of a wide range of antiferroelectrics.« less

Designing Pb-free relaxors with both a high capacitive energy density (W_rec) and high storage efficiency (η) remains a remarkable challenge for cutting-edge pulsed power technologies. Local compositional heterogeneity is crucial for achieving complex polar structure in solid solution relaxors, but its role in optimizing energy storage properties is often overlooked. Here, in this paper, we report that an exceptionally high W_rec of 15.2 J cm^–3 along with an ultrahigh η of 91% can be achieved through designing local chemical clustering in Bi_0.5Na_0.5TiO₃–BaTiO₃-based relaxors. A three-dimensional atomistic model derived from neutron/X-ray total scattering combined with reverse Monte Carlo method reveals themore » presence of subnanometer scale clustering of Bi, Na, and Ba, which host differentiated polar displacements, and confirming the prediction by density functional theory calculations. This leads to a polar state with small polar clusters and strong length and direction fluctuations in unit-cell polar vectors, thus manifesting improved high-field polarizability, steadily reduced hysteresis, and high breakdown strength macroscopically. The favorable polar structure features also result in a unique field-increased η, excellent stability, and superior discharge capacity. Our work demonstrates that the hidden local chemical order exerts a significant impact on the polarization characteristic of relaxors, and can be exploited for accessing superior energy storage performance.« less

Dielectric capacitors have captured substantial attention for advanced electrical and electronic systems. Developing dielectrics with high energy density and high storage efficiency is challenging owing to the high compositional diversity and the lack of general guidelines. Herein, we propose a map that captures the structural distortion ($$\delta$$) and tolerance factor (t) of perovskites to design Pb-free relaxors with extremely high capacitive energy storage. Our map shows how to select ferroelectric with large $$\delta$$ and paraelectric components to form relaxors with a t value close to 1 and thus obtaining eliminated hysteresis and large polarization under a high electric breakdown. Takingmore » the Bi_0.5Na_0.5TiO₃-based solid solution as an example, we demonstrate that composition-driven predominant order-disorder characteristic of local atomic polar displacements endows the relaxor with a slushlike structure and strong local polar fluctuations at several nanoscale. This leads to a giant recoverable energy density of 13.6 J cm^-3, along with an ultrahigh efficiency of 94%, which is far beyond the current performance boundary reported in Pb-free bulk ceramics. In conclusion, our work provides a solution through rational chemical design for obtaining Pb-free relaxors with outstanding energy-storage properties.« less

Large polarization and strain change during antiferroelectric - ferroelectric phase transition under electric field is the foundation for realizing excellent electrical properties in antiferroelectric ceramics, therefore, the adjustment of antiferroelectricity and clarification of the corresponding mechanism is the foundation for controlling electrical properties. NaNbO3 is the most complex perovskite system showing multiple antiferroelectric phases in a wide temperature range, in which the antiferroelectricity shows obvious instability with changing external and internal conditions, namely the antiferroelectric phase can be adjusted by grain-size effect, electric field and heat treatment. According to the systematical study in terms of the Rietveld refinement of synchrotronmore » XRD and Raman, NaNbO3 exhibits a ferrielectric P21ma structure at room temperature, the ferroelectric component of which increases with decreasing grain size. Two antiferroelectric tetragonal phases exist around Curie temperature TC before the entrance of antiferroelectric R phase zone, while an antiferroelectric monoclinic phase, which can be maintained to room temperature by annealing treatment, acts as the bridge for the depolarization of the poled NaNbO3 with ferroelectric Q phase. A detailed phase diagram mainly focused on the antiferroelectric phase zones of NaNbO3 is plotted, which gives a clear understanding about the polymorphic phase transitions under different conditions. Finally, the results concluded in this work would give a clear guidance for designing high-performance NaNbO3-based lead-free ceramics from the point of structure.« less

Chemical design of lead-free relaxors with simultaneously high energy density (W_rec) and high efficiency (η) for capacitive energy-storage has been a big challenge for advanced electronic systems. The current situation indicates that realizing such superior energy-storage properties requires highly complex chemical components. Herein, we demonstrate that, via local structure design, an ultrahigh W_rec of 10.1 J/cm³, concurrent with a high η of 90%, as well as excellent thermal and frequency stabilities can be achieved in a relaxor with a very simple chemical composition. By introducing 6s² lone pair stereochemical active Bi into the classical BaTiO₃ ferroelectric to generate a mismatchmore » between A- and B-site polar displacements, a relaxor state with strong local polar fluctuations can be formed. Through advanced atomic-resolution displacement mapping and 3D reconstructing the nanoscale structure from neutron/X-ray total scattering, it is revealed that the localized Bi enhances the polar length largely at several perovskite unit cells and disrupts the long-range coherent Ti polar displacements, resulting in a slush-like structure with extremely small size polar clusters and strong local polar fluctuations. This favorable relaxor state exhibits substantially enhanced polarization, and minimized hysteresis at a high breakdown strength. This work offers a feasible avenue to chemically design new relaxors with a simple composition for high-performance capacitive energy-storage.« less

Relaxor ferroelectrics are known for outstanding piezoelectric properties, finding a broad range of applications in advanced electromechanical devices. Decoding the origins of the enhanced properties, however, have long been complicated by the heterogeneous local structures. Here, we employ the advanced big-box refinement method by fitting neutron-, X-ray-based total scattering, and X-ray absorption spectrum simultaneously, to extract local atomic polar displacements and construct 3D polar configurations in the classical relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃. Our results demonstrate that prevailing order-disorder character accompanied by the continuous rotation of local polar displacements commands the composition-driven global structure evolution. The omnidirectional local polar disordering appears asmore » an indication of macroscopic relaxor characteristics. Combined with phase-field simulations, it demonstrates that the competing local polar order-disorder between different states with balanced local polar length and direction randomness leads to a flattening free-energy profile over a wide polar length, thus giving rise to high piezoelectricity. Our work clarifies that the critical structural feature required for high piezoelectricity is the competition states of local polar rather than relaxor.« less