Atomic-scale observations of electrical and mechanical manipulation of topological polar flux closure.

The ability to controllably manipulate complex topological polar configurations such as polar flux-closures via external stimuli may allow the construction of new electromechanical and nanoelectronic devices. Here, using atomically resolved in situ scanning transmission electron microscopy, we find that the polar flux-closures in PbTiO3/SrTiO3 superlattice films are mobile and can be reversibly switched to ordinary single ferroelectric c or a domains under an applied electric field or stress. Specifically, the electric field initially drives movement of a flux-closure via domain wall motion and then breaks it to form intermediate a/c striped domains, whereas mechanical stress first squeezes the core of a flux-closure toward the interface and then form a/c domains with disappearance of the core. After removal of the external stimulus, the flux-closure structure spontaneously recovers. These observations can be precisely reproduced by phase field simulations, which also reveal the evolutions of the competing energies during phase transitions. Such reversible switching between flux-closures and ordinary ferroelectric states provides a foundation for potential electromechanical and nanoelectronic applications.

Dynamics of Polar Skyrmion Bubbles under Electric Fields.

Room-temperature polar skyrmions, which have been recently discovered in oxide superlattice, have received considerable attention for their potential applications in nanoelectronics owing to their nanometer size, emergent chirality, and negative capacitance. For practical applications, their manipulation using external stimuli is a prerequisite. Herein, we study the dynamics of individual polar skyrmions at the nanoscale via in situ scanning transmission electron microscopy. By monitoring the electric-field-driven creation, annihilation, shrinkage, and expansion of topological structures in real space, we demonstrate the reversible transformation among skyrmion bubbles, elongated skyrmions, and monodomains. The underlying mechanism and interactions are discussed in conjunction with phase-field simulations. The electrical manipulation of nanoscale polar skyrmions allows the tuning of their dielectric permittivity at the atomic scale, and the detailed knowledge of their phase transition behaviors provides fundamentals for their applications in nanoelectronics.

Comparing Xe+ pFIB and Ga+ FIB for TEM sample preparation of Al alloys: Minimising FIB-induced artefacts.

Recently, the dual beam Xe+ plasma focused ion beam (Xe+ pFIB) instrument has attracted increasing interest for site-specific transmission electron microscopy (TEM) sample preparation for a local region of interest as it shows several potential benefits compared to conventional Ga+ FIB milling. Nevertheless, challenges and questions remain especially in terms of FIB-induced artefacts, which hinder reliable S/TEM microstructural and compositional analysis. Here we examine the efficacy of using Xe+ pFIB as compared with conventional Ga+ FIB for TEM sample preparation of Al alloys. Three potential source of specimen preparation artefacts were examined, namely: (1) implantation-induced defects such as amophisation, dislocations, or 'bubble' formation in the near-surface region resulting from ion bombardment of the sample by the incident beam; (2) compositional artefacts due to implantation of the source ions and (3) material redeposition due to the milling process. It is shown that Xe+ pFIB milling is able to produce improved STEM/TEM samples compared to those produced by Ga+ milling, and is therefore the preferred specimen preparation route. Strategies for minimising the artefacts induced by Xe+ pFIB and Ga+ FIB are also proposed. LAY DESCRIPTION: FIB (focused ion beam) instruments have become one of the most important systems in the preparation of site-specific TEM specimens, which are typically 50-100 nm in thickness. TEM specimen preparation of Al alloys is particularly challenging, as convention Ga-ion FIB produces artefacts in these materials that make microstructural analysis difficult or impossible. Recently, the use of noble gas ion sources, such as Xe, has markedly improved milling speeds and is being used for the preparation of various materials. Hence, it is necessary to investigate the structural defects formed during FIB milling and assess the ion-induced chemical contamination in these TEM samples. Here we explore the feasibility and efficiency of using Xe+ PFIB as a TEM sample preparation route for Al alloys in comparison with the conventional Ga+FIB.

Rapid growth of large area graphene on glass from olive oil by laser irradiation.

Although homogeneous, high quality graphene can be fabricated on a Cu or Ni sheet using the traditional chemical vapour deposition method at high temperatures (over 1000 °C) under specific atmospheric conditions, their transfer to another substrate is difficult. In this paper a novel method of rapidly (i.e. 3-6 s of laser irradiation) producing a large area (>3 cm2) graphene film from olive oil on a glass surface (pre-coated with a 5-28 nm thick Ni film) with defocused, large area continuous laser irradiation is described. The turbostratic graphene film (6 layers) grown in such a way has shown high electrical conductivity (sheet resistance of around 20 Ω sq-1) and an optical transmittance of 40-50%. With femtosecond laser patterning, 70% optical transparency was demonstrated. Continuous large area graphene was formed at relatively lower temperatures (<250 °C) and without the need for specific atmospheric conditions. The basic process characteristics and mechanisms involved are discussed.

Negative differential resistance effect in resistive switching devices based on h-LuFeO3/CoFe2O4 heterojunctions.

The negative differential resistance (NDR) effect enables multilevel storage and gradual resistance modulation in resistive switching (RS) devices to be achieved. However, the poor reproducibility of NDR is the obstacle that restricts their application because the appearance of the NDR effect in RS devices is usually accidental or unstable at room temperature. In this report, we demonstrate a polarization and interfacial defect modulated NDR effect in h-LuFeO3/CoFe2O4 heterojunction-based RS devices; especially, the NDR is reproducible after hundreds of cycles at room temperature. This research provides an effective way for realizing the reproducible NDR effect in ferroelectric RS devices, and it may promote the development and application of RS devices with the NDR effect.

The total dose effect of γ-ray induced domain evolution on α-In2Se3 nanoflakes.

Two-dimensional ferroelectric materials can maintain stable polarization with atomic layer thickness, and they have a wide range of technological applications in transistors, resistive memories, energy collectors and other multi-functional sensors for highly integrated flexible electronics. Domain evolution should be considered when 2d ferroelectric material-based devices are applied in a radiation environment, which may induce radiation damage and performance degradation. In this work, we investigate the domain evolution and photodetection performance degradation of α-In2Se3 nanoflakes induced by the total dose effect of 60Co γ-rays. The phonon modes change with an increase in total dose, while the domain structure changes in α-In2Se3 based transistors. Domain evolution may be one of the main reasons for the photoresponsivity degradation of these transistors. This investigation can provide a solid base for future research, and immediate applications in 2d ferroelectric material-based devices can be contemplated.

A neutron irradiation-induced displacement damage of indium vacancies in α-In2Se3 nanoflakes.

The discovery of layered two-dimensional (2D) ferroelectric materials has promoted the development of miniaturized and highly integrated ferroelectric electronics. The 2D ferroelectric materials can be applied in a radiation environment, in which the effect of radiation on these materials should be considered. However, the effects of radiation on 2D ferroelectric materials may be entirely different from those on traditional ferroelectric materials. Ionization effect-induced domain switching can be recovered by applying an external electric field, whereas the displacement effect initiated by radiation particles produces crystal structure damage. The displacement damage that is extremely difficult to recover may have a negative impact on the application of 2D ferroelectric materials in a radiation environment. In this study, the effect of displacement induced by neutron irradiation on the promising α-In2Se3 nanoflakes was investigated. Neutron irradiation (1 MeV) with a fluence of 1014 cm-2 was used for avoiding ionization effects in a certain range. Although the topography of α-In2Se3 does not change underneutron irradiation, vacancies have been proved to be induced by neutron irradiation; furthermore, it has been identified that the vacancies mostly originate from the loss of In atoms. The out-of-plane (OOP) and in-plane (IP) domain structures of the α-In2Se3 nanoflakes with a few layers only slighlty change. In addition, the polarization of the irradiated nanoflakes could still be reversed. All these findings show that although the vacancies may influence the band structure and polarizaiton values of α-In2Se3, the ferroelectric performance may have a strong resistance to neutron irradiation. Therefore, our investigation implies that α-In2Se3 is an excellent 2D ferroelectric material for application in radiation-resistant electronic devices in the future.

Enhanced electromagnon excitations in Nd-doped BiFeO3 nanoparticles near morphotropic phase boundaries.

In multiferroics, electromagnons have been recognized as a noticeable topic due to their indispensable role in magnetoelectric, magnetodielectric, and magnetocapacitance effects. Here, the electromagnons of Bi1-xNdxFeO3 (x = 0-0.2) nanoparticles are studied via terahertz time-domain spectroscopy, and the impacts of doping concentrations on electromagnons have been discussed. We found that the electromagnons in Bi1-xNdxFeO3 nanoparticles are associated with their phase transition. The total coupling weight of electromagnons is gradually increased in polar R3c structures and then reduces in the antipolar Pbam phase, and the weight in the antipolar phase is less than that of the pure R3c phase. Interestingly, a colossal electromagnon is observed at polar-antipolar and antiferromagnetic-ferromagnetic phase boundaries. Our work offers an avenue for designing and choosing materials with better magnetodielectric and magnetocapacitance properties.

Laser Direct Writing of Heteroatom (N and S)-Doped Graphene from a Polybenzimidazole Ink Donor on Polyethylene Terephthalate Polymer and Glass Substrates.

In this paper, for the first time, a laser direct writing technique is reported to form S- and N-doped graphene patterns on thin (0.3 mm thickness) polyethylene terephthalate (PET) and glass substrates from a specially formulated organic polybenzimidazole (PBI) ink, without thermally affecting the substrates and without the need for a metallic precursor. Unlike standard graphene ink printing, postcuring at high temperatures is not needed here, thus avoiding potential substrate distortion and damages. A UV laser beam of 355 nm wavelength is used to generate photochemical reactions to break the CS bond (2.8 eV) from dimethyl sulfoxide (DMSO, a component of the PBI ink) and the CN bond (3.14 eV) of PBI and form N- and S-doped graphene on the substrates. The sheet resistance of the laser-induced graphene is as low as 12 Ω sq-1 on PET, matching that of indium-tin oxide (ITO). The laser-written doped graphene shows hydrophilic characteristics, unlike pristine graphene. The S- and N-doped graphene allows the tailoring of bandgaps and thus controlling electrical and chemical properties. The optical transparency of the written graphene is below 10% which could be improved in the future. Potential applications include printing of flexible circuits and sensors, and smart wearables.

Precursor-Led Grain Boundary Engineering for Superior Thermoelectric Performance in Niobium Strontium Titanate.

We present a novel method to significantly enhance the thermoelectric performance of ceramics in the model system SrTi0.85Nb0.15O3 through the use of the precursor ammonium tetrathiomolybdate (0.5-2% w/w additions). After sintering the precursor-infused green body at 1700 K for 24 h in 5% H2/Ar, single-crystal-like electron transport behavior developed with electrical conductivity reaching ∼3000 S/cm at ∼300 K, almost a magnitude higher than that in the control sample. During processing, the precursor transformed into MoS2, then into MoOx, and finally into Mo particles. This limited grain growth promoted secondary phase generation but importantly helped to reduce the grain boundary barriers. Samples prepared with additions of the precursor exhibited vastly increased electrical conductivity, without significant impact on Seebeck coefficients giving rise to high power factor values of 1760 µW/mK2 at ∼300 K and a maximum thermoelectric figure-of-merit zT of 0.24 at 823 K. This processing strategy provides a simple method to achieve high charge mobility in polycrystalline titanate and related materials and with the potential to create "phonon-glass-electron-crystal" oxide thermoelectric materials.

High Power Factor Nb-Doped TiO2 Thermoelectric Thick Films: Toward Atomic Scale Defect Engineering of Crystallographic Shear Structures.

Donor-doped TiO2-based materials are promising thermoelectrics (TEs) due to their low cost and high stability at elevated temperatures. Herein, high-performance Nb-doped TiO2 thick films are fabricated by facile and scalable screen-printing techniques. Enhanced TE performance has been achieved by forming high-density crystallographic shear (CS) structures. All films exhibit the same matrix rutile structure but contain different nano-sized defect structures. Typically, in films with low Nb content, high concentrations of oxygen-deficient {121} CS planes are formed, while in films with high Nb content, a high density of twin boundaries are found. Through the use of strongly reducing atmospheres, a novel Al-segregated {210} CS structure is formed in films with higher Nb content. By advanced aberration-corrected scanning transmission electron microscopy techniques, we reveal the nature of the {210} CS structure at the nano-scale. These CS structures contain abundant oxygen vacancies and are believed to enable energy-filtering effects, leading to simultaneous enhancement of both the electrical conductivity and Seebeck coefficients. The optimized films exhibit a maximum power factor of 4.3 × 10-4 W m-1 K-2 at 673 K, the highest value for TiO2-based TE films at elevated temperatures. Our modulation strategy based on microstructure modification provides a novel route for atomic-level defect engineering which should guide the development of other TE materials.

Self-Recovery of a Buckling BaTiO3 Ferroelectric Membrane.

The characteristic of self-recovery holds significant implications for upholding performance stability within flexible electronic devices following the release of mechanical deformation. Herein, the dynamics of self-recovery in a buckling inorganic membrane is studied via in situ scanning probe microscopy technology. The experimental results demonstrate that the ultimate deformation ratio of the buckling BaTiO3 ferroelectric membrane is up to 88%, which is much higher than that of the buckling SrTiO3 dielectric membrane (49%). Combined with piezoresponse force microscopy and phase-field simulations, we find that ferroelectric domain transformation accompanies the whole process of buckling and self-recovery of the ferroelectric membrane, i.e., the presence of the nano-c domain not only releases part of the elastic energy of the membrane but also reduces the interface mismatch of the a/c domain, which encourages the buckling ferroelectric membrane to have excellent self-recovery properties. It is conceivable that the evolution of ferroelectric domains will play a greater role in the regulation of the mechanical properties of ferroelectric membranes and flexible devices.

Synthesis of High Entropy and Entropy-Stabilized Metal Sulfides and Their Evaluation as Hydrogen Evolution Electrocatalysts.

High entropy metal chalcogenides are materials containing five or more elements within a disordered sublattice. These materials exploit a high configurational entropy to stabilize their crystal structure and have recently become an area of significant interest for renewable energy applications such as electrocatalysis and thermoelectrics. Herein, we report the synthesis of bulk particulate HE zinc sulfide analogues containing four, five, and seven metals. This was achieved using a molecular precursor cocktail approach with both transition and main group metal dithiocarbamate complexes which are decomposed simultaneously in a rapid (1 h) and low-temperature (500 °C) thermolysis reaction to yield high entropy and entropy-stabilized metal sulfides. The resulting materials were characterized by powder XRD, SEM, and TEM, alongside EDX spectroscopy at both the micro- and nano-scales. The entropy-stabilized (CuAgZnCoMnInGa)S material was demonstrated to be an excellent electrocatalyst for the hydrogen evolution reaction when combined with conducting carbon black, achieving a low onset overpotential of (∼80 mV) and η10 of (∼255 mV).

Synergistic effect of Si concentration and distribution on ferroelectric properties optimization of Si:HfO2ferroelectric thin films.

In this paper, a phase-field model of Si-doped hafnium oxide-based ferroelectric thin films is established. And then, the synergistic effect of Si concentration and distribution on ferroelectric properties optimization of Si:HfO2ferroelectric thin films is studied with the proposed model. It is found that no matter how Si dopant is distributed in the film, the volume fraction of the ferroelectric phase in the film increases first and then decreases with the increase of Si concentration. However, compared with the uniform distribution, the layered distribution is more likely to great improve ferrelectric properties. When Si dopant is uniformly distributed in the film, the highest remanent polarization value that the film can obtain via Si concentration modulation is 38.7µC cm-2, and the corresponding Si concentration is 3.8 cat%, which is consistent with the experimental results. When Si dopant is layered in the film, and the concentration difference between the Si-rich and Si-poor layers is 7.6%, in the Si concentration range of 3.6 cat%-3.8 cat%, the residual polarization of the film reaches 46.4-46.8µC cm-2, which is 20% higher than that when Si dopant are evenly distributed in the film. The above results show that selecting the Si layered distribution mode and controlling the concentration difference between Si-rich and Si-poor layers in an appropriate range can greatly improve the films' ferroelectric properties and broaden the Si concentration optimization range of the ferroelectric properties of the films. The result provides further theoretical guidance on using Si doping to adjust the ferroelectric properties of hafnium oxide-based films.

Robustly Stable Ferroelectric Polarization States Enable Long-Term Nonvolatile Storage against Radiation in HfO2-Based Ferroelectric Field-Effect Transistors.

The ferroelectric field-effect transistors (FeFETs) with HfO2-based ferroelectric layers in the gate stacks are emerging as one of the most promising candidates for the next-generation nonvolatile memory devices due to their scalability and compatibility with conventional Si technology. Moreover, owing to the high radiation hardness of the HfO2-based ferroelectric thin films, HfO2-based FeFETs have attracted great interest in the fields of radiation-hard (rad-hard) memory. However, the reliability of their memory states under irradiation, which represents the validity of the stored information, has not been investigated. Here, we focus on the impact of the total ionizing dose (TID) on erased and programmed states of HfO2-based FeFETs. The TID radiation (X-ray) characteristics of erased and programmed HfO2-based FeFETs are characterized using an on-site read operation. Both the erased and programmed states show robust stability under irradiation at a dose rate of 90 rad(Si)/s, and even at 230 rad(Si)/s, only the erased state shows a slight variation. The possible factors contributing to memory state degradation are discussed. Through the analysis of the threshold voltage shift and subthreshold swing evolution, as well as studies of ferroelectric polarization stability under radiation, it is revealed that the erased state degradation is caused by oxide-trapped charges rather than interface degradation or polarization switching. The physical mechanism of the difference in radiation-induced oxide-trapped charges buildup in programmed and erased FeFETs is analyzed to explain different TID radiation characteristics between them. Our work suggests that the HfO2-based FeFETs have great potential in radiation environment applications.

Inhibiting weld cracking in high-strength aluminium alloys.

Cracking from a fine equiaxed zone (FQZ), often just tens of microns across, plagues the welding of 7000 series aluminum alloys. Using a multiscale correlative methodology, from the millimeter scale to the nanoscale, we shed light on the strengthening mechanisms and the resulting intergranular failure at the FQZ. We show that intergranular AlCuMg phases give rise to cracking by micro-void nucleation and subsequent link-up due to the plastic incompatibility between the hard phases and soft (low precipitate density) grain interiors in the FQZ. To mitigate this, we propose a hybrid welding strategy exploiting laser beam oscillation and a pulsed magnetic field. This achieves a wavy and interrupted FQZ along with a higher precipitate density, thereby considerably increasing tensile strength over conventionally hybrid welded butt joints, and even friction stir welds.

Probing Ultrafast Dynamics of Ferroelectrics by Time-Resolved Pump-Probe Spectroscopy.

Ferroelectric materials have been a key research topic owing to their wide variety of modern electronic and photonic applications. For the quick exploration of higher operating speed, smaller size, and superior efficiencies of novel ferroelectric devices, the ultrafast dynamics of ferroelectrics that directly reflect their respond time and lifetimes have drawn considerable attention. Driven by time-resolved pump-probe spectroscopy that allows for probing, controlling, and modulating dynamic processes of ferroelectrics in real-time, much research efforts have been made to understand and exploit the ultrafast dynamics of ferroelectric. Herein, the current state of ultrafast dynamic features of ferroelectrics tracked by time-resolved pump-probe spectroscopy is reviewed, which includes ferroelectrics order parameters of polarization, lattice, spin, electronic excitation, and their coupling. Several potential perspectives and possible further applications combining ultrafast pump-probe spectroscopy and ferroelectrics are also presented. This review offers a clear guidance of ultrafast dynamics of ferroelectric orders, which may promote the rapid development of next-generation devices.

Highly Ordered SnO2 Nanopillar Array as Binder-Free Anodes for Long-Life and High-Rate Li-Ion Batteries.

SnO2, a typical transition metal oxide, is a promising conversion-type electrode material with an ultrahigh theoretical specific capacity of 1494 mAh g-1. Nevertheless, the electrochemical performance of SnO2 electrode is limited by large volumetric changes (~300%) during the charge/discharge process, leading to rapid capacity decay, poor cyclic performance, and inferior rate capability. In order to overcome these bottlenecks, we develop highly ordered SnO2 nanopillar array as binder-free anodes for LIBs, which are realized by anodic aluminum oxide-assisted pulsed laser deposition. The as-synthesized SnO2 nanopillar exhibit an ultrahigh initial specific capacity of 1082 mAh g-1 and maintain a high specific capacity of 524/313 mAh g-1 after 1100/6500 cycles, outperforming SnO2 thin film-based anodes and other reported binder-free SnO2 anodes. Moreover, SnO2 nanopillar demonstrate excellent rate performance under high current density of 64 C (1 C = 782 mA g-1), delivering a specific capacity of 278 mAh g-1, which can be restored to 670 mAh g-1 after high-rate cycling. The superior electrochemical performance of SnO2 nanoarray can be attributed to the unique architecture of SnO2, where highly ordered SnO2 nanopillar array provided adequate room for volumetric expansion and ensured structural integrity during the lithiation/delithiation process. The current study presents an effective approach to mitigate the inferior cyclic performance of SnO2-based electrodes, offering a realistic prospect for its applications as next-generation energy storage devices.

High Energy Performance Ferroelectric (Ba,Sr)(Zr,Ti)O3 Film Capacitors Integrated on Si at 400 °C.

BaTiO3-based ferroelectrics have been extensively studied due to their large dielectric constants and a high saturated polarization, which have the potential to store or supply electricity of very high energy and power densities. In order to further improve the energy efficiency η and the recyclable energy density Wrec, an A, B-site co-doped (Ba0.95,Sr0.05)(Zr0.2,Ti0.8)O3 ceramic target was used for sputter deposition of film capacitor structures on Si. This film composition reduces the remnant polarization Pr, while the choice of a low-temperature, templated sputtering process facilitates the formation of high-density arrays of columnar nanograins (average diameter d ∼20 nm) and grain boundary dead layers. This self-assembled nanostructure further delays the saturation of the electric polarization, leading to a high energy density Wrec of ∼148 J/cm3 and a high energy efficiency η of ∼90%. Moreover, the (Ba0.95,Sr0.05)(Zr0.2,Ti0.8)O3 film capacitors retain their high energy storage performance in a broad range of working temperature (-175-300 °C) and operating frequency (1 Hz-20 kHz). They are also fatigue-free after up to 2 × 109 switching cycles. Our work provides a new method and a cost-effective processing route for the creation and integration of high-performance dielectric capacitors for energy storage applications.