Remarkable Piezophoto Coupling Catalysis Behavior of BiOX/BaTiO3 (X = Cl, Br, Cl0.166 Br0.834 ) Piezoelectric Composites.

Polarization field engineering of piezoelectric materials is considered as an advisable strategy in fine-tuning photocatalytic performance which has drawn much attention recently. However, the efficient charge separation that determines the photocatalytic reactivities of these materials is quite restricted. Herein, a judicious combination of piezoelectric and photocatalytic performances of BiOX/BaTiO3 (X = Cl, Br, Cl0.166 Br0.834 ) to enable a high piezophotocatalytic activity is demonstrated. Under the synergic advantages of chemical potential difference and piezoelectric potential difference in BiOX/BaTiO3 composites, the photoinduced carriers recombination is largely halted, which directly contributes to the significantly promoted piezophotocatalytic activity of piezoelectric composites. Inspiringly, the BiOBr/BaTiO3 composites under light irradiation with auxiliary ultrasonic activation result in an ultrahigh and stable photocatalytic performance, which is much higher than the total of those by isolated photocatalysis and piezocatalysis, and can rival current excellent photocatalytic system. In fact, the theoretical piezoelectric potential difference of BiOBr/BaTiO3 composites reaches 100 mV, which far exceeds the pure BaTiO3 of 31.21 mV and BiOBr of 30 mV, respectively. First, fabrication of BiOX/BaTiO3 piezoelectric composites and its remarkable piezophoto coupling catalysis behavior lays new ground for developing high-efficiency piezoelectric photocatalysts in purifying wastewater, killing bacteria, and other piezophototronic processes.

Ultra-large electromechanical deformation in lead-free piezoceramics at reduced thickness.

Lead-free piezoceramics with large controllable deformations are highly desirable for numerous energy converter applications ranging from consumer electronics to medical microrobots. Although several new classes of high-performance ferroelectrics have been discovered, a universal strategy to enable various piezoceramics to realize large electromechanical deformations is still lacking. Herein, by gradually reducing the thickness from 0.5 mm to 0.1 mm, we discover that a large nominal electrostrain of ∼11.49% can be achieved in thin 0.937(Bi0.5Na0.5)TiO3-0.063BaTiO3 (BNT-BT) ceramics with highly asymmetric strain-electric field curves. Further analyses of the polarization switching process reveal that the boosted strain curves originate from the bending deformation driven by asymmetric ferroelastic switching in the surface layers. Based on this, one monolayer BNT-BT was designed to realize digital displacement actuation and a scanning mirror application with a maximum mirror deflection angle of 44.38°. Moreover, the surface effect-induced bending deformation can be extended to other piezoceramics, accompanied by derived shape retention effects. These discoveries raise the possibility of utilizing thickness engineering to design large-displacement actuators and may accelerate the development of high-performance lead-free piezoceramics.

Nanoscale Thermal Strain Engineering-Driven Ferroelastic Domain Evolution in CH3NH3PbI3 Perovskites.

A local thermal strain engineering approach via an ac-heated thermal probe was incorporated into methylammonium lead triiodide (MAPbI3) crystals and acts as a driving force for ferroic twin domain dynamics, local ion migration, and property tailoring. Periodically, striped ferroic twin domains and their dynamic evolutions were successfully induced by local thermal strain and high-resolution thermal imaging, giving decisive evidence of the ferroelastic nature in MAPbI3 perovskites at room temperature. Local thermal ionic imaging and chemical mappings demonstrate that domain contrasts are from local methylammonium (MA+) redistribution into the stripes of chemical segregation in response to the local thermal strain fields. The present results reveal an inherent coupling among local thermal strains, ferroelastic twin domains, local chemical-ion segregations, and physical properties and offer a potential path to improve the functionality of metal halide perovskite-based solar cells.

High-Energy Storage Properties over a Broad Temperature Range in La-Modified BNT-Based Lead-Free Ceramics.

The development of high-performance energy storage materials is decisive for meeting the miniaturization and integration requirements in advanced pulse power capacitors. In this study, we designed high-performance [(Bi0.5Na0.5)0.94Ba0.06](1-1.5x)LaxTiO3 (BNT-BT-xLa) lead-free energy storage ceramics based on their phase diagram. A strategy combining phase adjustment and domain control via doping was proposed to enhance the energy storage performance. The obtained results showed that La3+ ions doped into BNT-BT improved the crystal structure symmetry and induced a strong dielectric relaxation behavior, which destroyed the long-term ferroelectric order and effectively promoted the formation of polar nanoregions. At x = 0.12, a high recoverable energy density (Wrec) of ∼5.93 J/cm3 and a relatively large energy storage efficiency (η) of 77.6% were obtained under a high breakdown electric field of 440 kV/cm. By using a two-step sintering approach for the microstructural optimization, the energy storage performance was further improved, yielding much higher Wrec (6.69 J/cm3) and η (87.0%). Additionally, both conventionally sintered and two-step-sintered samples showed excellent frequency stability (0.5-500 Hz), thermal endurance (25-180 °C), and fatigue resistance (105 cycles). Regarding the pulse charge-discharge performance, the samples exhibited ultrashort discharge time (t0.9 ∼ 89 ns for the conventionally sintered sample and ∼75 ns for the two-step-sintered sample) under an electric field of 240 kV/cm. Furthermore, the breakdown process of the material was simulated based on the finite element analysis, and it was shown that high breakdown strength of the material could be ascribed to fine grains, which significantly hindered the crack propagation during the application of the electric field. These results show that the presented materials have great potential as high-energy storage capacitors.

Novel Ultrahigh-Performance ZnO-Based Varistor Ceramics.

The nonlinear response of a material to an external stimulus is vital in fundamental science and technical applications. The power-law current-voltage relationship of a varistor is one such example. An excellent example of such behavior is the power-law current-voltage relationship exhibited by Bi2O3-doped ZnO varistor ceramics, which are the cornerstone of commercial varistor materials for overvoltage protection. Here, we report on a sustainable, ZnO-based varistor ceramic, without the volatile Bi2O3, that is based on Cr2O3 as the varistor former and oxides of Ca, Co, and Sb as the performance enhancers. The material has an ultrahigh α of up to 219, a low IL of less than 0.2 µA/cm2, and a high Eb of up to 925 V/mm, making it superior to state-of-the-art varistor ceramics. The results provide insights into the design of materials with specific characteristics by tailoring states at the grain boundaries. The discovery of this ZnO-Cr2O3-type varistor ceramic represents a major breakthrough in the field of varistors for overvoltage protection and could drastically affect the world market for overvoltage protection.

AFM-IR probing the influence of polarization on the expression of proteins within single macrophages.

Macrophages are essential in innate immunity and are involved in a variety of biological functions. Due to high plasticity, macrophages are polarized in different phenotypes depending on different microenvironments to perform specific functions. Although many studies have focused on macrophage polarization, few have explored the polarization characteristics of macrophages at the subcellular level, even at nanoscale resolution. Here, we utilize AFM-based infrared spectroscopy (AFM-IR) to investigate the influence of an inducer on the expressed proteins of M1/M2 macrophages (induced by LPS and IL-13, respectively). The results from AFM-IR combined with principal component analysis revealed that the characteristic proteins within M1 contain about 35% antiparallel ß-sheets (due to the high expression of TNF-α), while the proteins within M2 are made up of approximately 38.8% α-helices. The corresponding nanoscale chemical mapping demonstrates a remarkably heterogeneous distribution of expressed proteins inside single macrophages. Beside the biochemical properties, the biomechanical properties of macrophages were found to be softened in response to the polarization process.

Potential High-Temperature Piezoelectric Ceramics with Remarkable Performances Enhanced by the Second-Order Jahn-Teller Effect.

Herein, the second-order Jahn-Teller effect was applied to the design of the bismuth ferrite-based ceramics. A large distortion of an electron structure arranged along the z axis and an asymmetric distribution of charge density were calculated in 0.80(0.725BiFeO3-0.275BaTiO3)-0.20PT (0.20 PT) based on the density functional theory, indicating good ferro/piezoelectric properties. The top experimental polarization of 36.89 µC/cm2, optimal d33 value of 258 pC/N measured at room temperature, and ultrahigh d33 value of 303 pC/N measured at 370 °C were obtained at 0.20 PT, thereby further confirming the calculations. Furthermore, a high Curie point of 488 °C, as well as outstanding temperature stability ranging from room temperature to 430 °C of the 0.20 PT ceramic was observed. The domain of the 0.20 PT exhibited greater order and smaller size, resulting in easy switching when applying voltage. The distorted electron structure, plumb grains, ordered and easily switchable domains, and coexistences of tetragonal (T) and rhombohedral (R) phases contributed to the large piezoelectric constant of the 0.2 PT ceramic. BFBT-xPT ceramics are potentially promising for high-temperature piezoelectric field applications.

Thermal Conductivity during Phase Transitions.

Thermal conductivity is a very basic property that determines how fast a material conducts heat, which plays an important and sometimes a dominant role in many fields. However, because materials with phase transitions have been widely used recently, understanding and measuring temperature-dependent thermal conductivity during phase transitions are important and sometimes even questionable. Here, the thermal transport equation is corrected by including heat absorption due to phase transitions to reveal how a phase transition affects the measured thermal conductivity. In addition to the enhanced heat capacity that is well known, it is found that thermal diffusivity can be abnormally lowered from the true value, which is also dependent on the speed of phase transitions. The extraction of the true thermal conductivity requires removing the contributions from both altered heat capacity and thermal diffusivity during phase transitions, which is well demonstrated in four selected kinds of phase transition materials (Cu2 Se, Cu2 S, Ag2 S, and Ag2 Se) in experiment. This study also explains the lowered abnormal thermal diffusivity during phase transitions in other materials and thus provides a novel strategy to engineer thermal conductivity for various applications.

Anomalous Photovoltaic Effect in Centrosymmetric Ferroelastic BiVO4.

The anomolous photovoltaic (APV) effect is an intriguing phenomenon and rarely observed in bulk materials that structurally have an inversion symmetry. Here, the discovery of such an APV effect in a centrosymmetric vanadate, BiVO4, where noticeable above-bandgap photovoltage and a steady-state photocurrent are observed in both ceramics and single crystals even when illuminated under visible light, is reported. Moreover, the photovoltaic voltage can be reversed by the stress modulation, and a sine-function relationship between the photovoltage and stress directional angle is derived. Microstructure and strain-field analysis reveal localized asymmetries that are caused by strain fluctuations in bulk centrosymmetric BiVO4. On the basis of the experimental results, a flexoelectric coupling via a strain-induced local polarization mechanism is suggested to account for the APV effect observed. This work not only allows new applications for BiVO4 in optoelectronic devices but also deepens insights into the mechanisms underlying the APV effect.

Dynamic interfacial mechanical-thermal characteristics of atomically thin two-dimensional crystals.

Owing to the flexible nanoelectronic applications of two-dimensional (2D) materials, further exploration of their nanoscale local mechanical properties and their coupled physical characteristics becomes extremely significant. The puckering effect is a typical micro/nanoscale local frictional characteristic generally in the tip-film-substrate system, which is simultaneously expected to be coupled with a dynamic thermal interfacial response. Here, applying scanning thermal microscopy (SThM), we observed a novel mechanical-thermal coupling effect in monolayer/bilayer MoS2 and WS2 films: puckering deformation can induce the enhancement of interfacial thermal resistance (TR). By the SThM method, the puckering effect was further proved to depend on the film thickness and the scan velocity. More importantly, the crystallographic orientation-dependent anisotropy of the puckering effect in atomically thin two-dimensional crystals was demonstrated by SThM. It is inferred that the puckering deformation of the film redistributes the in-plane stress, resulting in the isotropy breaking of the in-plane stiffness. Such new findings are of great significance to help optimize the nanoscale tribological/thermal design and dynamic mechanical-thermal management of 2D-materials in nanoelectronics.

Alkali-assisted mild aqueous exfoliation for single-layered and structure-preserved graphitic carbon nitride nanosheets.

Single-layered g-C3N4 nanosheets have been fabricated by delaminating directly its bulk counterpart in an alkaline solution. According to the theoretical modeling, the interaction of OH- with terminal NH2 or bridged NH group of the triazine units within bulk g-C3N4 crystal structure could result in decreased bonding energy between layers and promote the total delamination. The resulting g-C3N4 nanosheets colloid has a relatively high concentration (12g/L) compared with the traditional ultrasonic assistant exfoliation method. The delaminated nanosheets are revealed by atomic force microscopy to show a lateral size of a hundred nanometers and a thickness of about 0.4nm, which provides a direct evidence for the total exfoliation of g-C3N4 crystals into their single sheets. More importantly, the X-ray diffraction measurement confirms that the g-C3N4 nanosheets could be re-assembled with well-preserved original crystal structure. The exfoliation mechanism was also confirmed by the DFT calculation.

Influence of Oxygen Pressure on the Domain Dynamics and Local Electrical Properties of BiFe0.95Mn0.05O3 Thin Films Studied by Piezoresponse Force Microscopy and Conductive Atomic Force Microscopy.

In this work, we have studied the microstructures, nanodomains, polarization preservation behaviors, and electrical properties of BiFe0.95Mn0.05O3 (BFMO) multiferroic thin films, which have been epitaxially created on the substrates of SrRuO3, SrTiO3, and TiN-buffered (001)-oriented Si at different oxygen pressures via piezoresponse force microscopy and conductive atomic force microscopy. We found that the pure phase state, inhomogeneous piezoresponse force microscopy (PFM) response, low leakage current with unidirectional diode-like properties, and orientation-dependent polarization reversal properties were found in BFMO thin films deposited at low oxygen pressure. Meanwhile, these films under high oxygen pressures resulted in impurities in the secondary phase in BFMO films, which caused a greater leakage that hindered the polarization preservation capability. Thus, this shows the important impact of the oxygen pressure on modulating the physical effects of BFMO films.