RESUMEN
Unlike metals where dislocations carry strain singularity but no charge, dislocations in oxide ceramics are characterized by both a strain field and a local charge with a compensating charge envelope. Oxide ceramics with their deliberate engineering and manipulation are pivotal in numerous modern technologies such as semiconductors, superconductors, solar cells, and ferroics. Dislocations facilitate plastic deformation in metals and lead to a monotonous increase in the strength of metallic materials in accordance with the widely recognized Taylor hardening law. However, achieving the objective of tailoring the functionality of oxide ceramics by dislocation density still remains elusive. Here a strategy to imprint dislocations with {100}<100> slip systems and a tenfold change in dislocation density of BaTiO3 single crystals using high-temperature uniaxial compression are reported. Through a dislocation density-based approach, dielectric permittivity, converse piezoelectric coefficient, and alternating current conductivity are tailored, exhibiting a peak at medium dislocation density. Combined with phase-field simulations and domain wall potential energy analyses, the dislocation-density-based design in bulk ferroelectrics is mechanistically rationalized. These findings may provide a new dimension for employing plastic strain engineering to tune the electrical properties of ferroics, potentially paving the way for advancing dislocation technology in functional ceramics.
RESUMEN
The internal electric field within a piezoelectric material can effectively inhibit the recombination of photogenerated electron-hole pairs, thus serving as a means to enhance photocatalytic efficiency. Herein, we synthesized a Na0.5Bi4.5Ti4O15 (NBT) catalyst by the hydrothermal method and optimized its catalytic performance by simple high-voltage poling. When applying light and mechanical stirring on a 2 kV mm-1 poled NBT sample, almost 100% of Rhodamine B solution could be degraded in 120 min, and the reaction rate constant reached as high as 28.36 × 10-3 min-1, which was 4.2 times higher than that of the unpoled NBT sample. The enhanced piezo-photocatalytic activity is attributed to the poling-enhanced internal electric field, which facilitates the efficient separation and transfer of photogenerated carriers. Our work provides a new option and idea for the development of piezo-photocatalysts for environmental remediation and pollutant treatment.
RESUMEN
We report an intrinsic strain engineering, akin to thin filmlike approaches, via irreversible high-temperature plastic deformation of a tetragonal ferroelectric single-crystal BaTiO_{3}. Dislocations well-aligned along the [001] axis and associated strain fields in plane defined by the [110]/[1[over ¯]10] plane are introduced into the volume, thus nucleating only in-plane domain variants. By combining direct experimental observations and theoretical analyses, we reveal that domain instability and extrinsic degradation processes can both be mitigated during the aging and fatigue processes, and demonstrate that this requires careful strain tuning of the ratio of in-plane and out-of-plane domain variants. Our findings advance the understanding of structural defects that drive domain nucleation and instabilities in ferroic materials and are essential for mitigating device degradation.
RESUMEN
Dislocations are usually expected to degrade electrical, thermal and optical functionality and to tune mechanical properties of materials. Here, we demonstrate a general framework for the control of dislocation-domain wall interactions in ferroics, employing an imprinted dislocation network. Anisotropic dielectric and electromechanical properties are engineered in barium titanate crystals via well-controlled line-plane relationships, culminating in extraordinary and stable large-signal dielectric permittivity (≈23100) and piezoelectric coefficient (≈2470 pm V-1). In contrast, a related increase in properties utilizing point-plane relation prompts a dramatic cyclic degradation. Observed dielectric and piezoelectric properties are rationalized using transmission electron microscopy and time- and cycle-dependent nuclear magnetic resonance paired with X-ray diffraction. Succinct mechanistic understanding is provided by phase-field simulations and driving force calculations of the described dislocation-domain wall interactions. Our 1D-2D defect approach offers a fertile ground for tailoring functionality in a wide range of functional material systems.
RESUMEN
The triboelectric effect is a ubiquitous phenomenon in which the surfaces of two materials are easily charged during the contact-separation process. Despite the widespread consequences and applications, the charging mechanisms are not sufficiently understood. Here, the authors report that, in the presence of a strain gradient, the charge transfer is a result of competition between flexoelectricity and triboelectricity, which could enhance charge transfer during triboelectric measurements when the charge transfers of both effects are in the same direction. When they are in the opposite directions, the direction and amount of charge transfer could be modulated by the competition between flexoelectric and triboelectric effects, which leads to a distinctive phenomenon, that is, the charge transfer is reversed with varying forces. The subsequent results on the electrical power output signals from the triboelectrification support the proposed mechanism. Therefore, the present study emphasizes the key role of the flexoelectric effect through experimental approaches, and suggests that both the amount and direction of charge transfer can be modulated by manipulating the mixed triboelectric and flexoelectric effects. This finding may provide important information on the triboelectric effect and can be further extended to serve as a guideline for material selection during a nanopatterned device design.
RESUMEN
Defects are essential to engineering the properties of functional materials ranging from semiconductors and superconductors to ferroics. Whereas point defects have been widely exploited, dislocations are commonly viewed as problematic for functional materials and not as a microstructural tool. We developed a method for mechanically imprinting dislocation networks that favorably skew the domain structure in bulk ferroelectrics and thereby tame the large switching polarization and make it available for functional harvesting. The resulting microstructure yields a strong mechanical restoring force to revert electric field-induced domain wall displacement on the macroscopic level and high pinning force on the local level. This induces a giant increase of the dielectric and electromechanical response at intermediate electric fields in barium titanate [electric field-dependent permittivity (ε33) ≈ 5800 and large-signal piezoelectric coefficient (d 33*) ≈ 1890 picometers/volt]. Dislocation-based anisotropy delivers a different suite of tools with which to tailor functional materials.
RESUMEN
As emerging materials for capacitor applications, antiferroelectric (AFE) materials possess high energy storage density. AFE single crystals are conducive to studying the physical mechanism of AFE response. However, the preparation of AFE single crystals is a huge and long-standing challenge. Herein, we report the effect of Na/La codoping on the energy storage properties and phase transition of Pb(Lu1/2Nb1/2)O3 (PLN) AFE single crystals. An enhanced recoverable energy storage density of 4.81 J/cm3 with a high energy efficiency of 82.36% is obtained, which is much larger than that of the PbZrO3- and PLN-based AFE crystals. Two superlattice reflections, which stem from the A-site Pb2+ ions and the ordered B-site ions, are identified by X-ray diffraction and selected-area electron diffraction. The domain structures demonstrated a high temperature stability of the AFE phase. A secondary ferroelectric phase transition is induced after codoping, resulting in a sharp improvement of polarization (12.5 µC/cm2), which contributes to the enormous enhancement of energy storage density. This multiphase transition is explained using the modified Ginzburg-Landau-Devonshire phenomenology.
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Antiferroelectric (AFE) materials have a tremendous advantage as smart materials and large-strain actuators due to their unique reversible characteristic electric-field-induced strain (electrostrain) responses in comparison to piezoelectric effect and electrostriction. A key limitation to today's AFE actuators, however, is the poor temperature stability of electrostrain. In this work, a large reversible strain of 0.4% and an excellent thermal stability with a variation within ±5.5% from 20 to 190 °C were achieved for (Pb0.97La0.02)(Zr0.85Sn0.08Ti0.07)O3 (PLZST) AFE ceramics. A room-temperature electrostrain of 0.71% was obtained in virgin PLZST ceramics. It is intriguing to observe inconsistent strain curves between the first and further measured cycles, implying an incomplete reversible field-induced AFE-ferroelectric phase transition. A sharp electrostrain response in milliseconds was realized in the as-prepared PLZST ceramics. In addition, a phenomenological explanation was proposed to explain the extraordinary phenomena. Our results may shed light on the origin of the superior strain behaviors in AFE materials from the view of microscopic structure and macroscopic properties, and probably improve the understanding of the AFE phase transition.
RESUMEN
(Pb0.97La0.02)(Zr xSn0.94- xTi0.06)O3 (PLZST) antiferroelectric ceramics with x = 0.75-0.90 have been fabricated and found to be a novel electrocaloric material system with a giant negative electrocaloric effect (Δ T = -11.5 K) and a large electrocaloric strength (|Δ T/Δ E| = 0.105 K cm kV-1) near room temperature. Additionally, the PLZST antiferroelectric ceramic also exhibits a large positive electrocaloric effect around the Curie temperature. The giant negative effect and the coexistence of both positive and negative electrocaloric effects in one material indicate a promising possibility to develop mid- to large-scale solid-state cooling devices with high efficiency.
RESUMEN
(Pb,La)(Zr,Sn,Ti)O3 (PLZST) single crystals with their chemical composition located at the tetragonal antiferroelectric region are grown via the flux method in a PbO-PbF2-B2O3 mixture. Segregation of the Ti4+ component in the as-grown crystals is observed due to the strong affinity between the oxygen anion and Ti4+ ions. The critical electric field of the antiferroelectric to ferroelectric phase transition is determined to be about 0.5 kV mm-1. The electric field induced ferroelectric phase transforms back into the antiferroelectric phase at a depolarization temperature of 125 °C. Anisotropy of the harvested energy density and electrocaloric behaviors are achieved for the [100], [110] and [111]-oriented PLZST crystals. Based on the thermodynamic theory approach, all the abovementioned behaviors originate from the anisotropic total entropy change. Enhanced electrocaloric strength (0.3 K mm kV-1) and the harvested energy density of 0.62 J cm-3 are obtained in the [111]-oriented PLZST crystals. Our results demonstrate the competence of PLZST single crystals for cooling devices and pyroelectric energy harvesting and provide new opportunities to improve energy harvesting density and electrocaloric properties via the anisotropic structural layout, which make the PLZST crystals attractive for solid state cooling devices and energy conversion technologies.