Stereo-Hindrance Engineering of A Cation toward <110>-Oriented 2D Perovskite with Minimized Tilting and High-Performance X-Ray Detection.

2D <100>-oriented Dion-Jacobson or Ruddlesden-Popper perovskites are widely recognized as promising candidates for optoelectronic applications. However, the large interlayer spacing significantly hinders the carrier transport. <110>-oriented 2D perovskites naturally exhibit reduced interlayer spacings, but the tilting of metal halide octahedra is typically serious and leads to poor charge transport. Herein, a <110>-oriented 2D perovskite EPZPbBr4 (EPZ = 1-ethylpiperazine) with minimized tilting is designed through A-site stereo-hindrance engineering. The piperazine functional group enters the space enclosed by the three [PbBr6 ]4- octahedra, pushing Pb─Br─Pb closer to a straight line (maximum Pb─Br─Pb angle ≈180°), suppressing the tilting as well as electron-phonon coupling. Meanwhile, the ethyl group is located between layers and contributes an extremely reduced effective interlayer distance (2.22 Å), further facilitating the carrier transport. As a result, EPZPbBr4 simultaneously demonstrates high µτ product (1.8 × 10-3 cm2 V-1 ) and large resistivity (2.17 × 1010 Ω cm). The assembled X-ray detector achieves low dark current of 1.02 × 10-10 A cm-2 and high sensitivity of 1240 µC Gy-1 cm-2 under the same bias voltage. The realized specific detectivity (ratio of sensitivity to noise current density, 1.23 × 108 µC Gy-1 cm-1 A-1/2 ) is the highest among all reported perovskite X-ray detectors.

Recent progress on defect-engineering in ferroelectric HfO2: The next step forward via multiscale structural optimization.

The discovery of unconventional scale-free ferroelectricity in HfO2-based fluorite thin films has attracted great attention in recent years for their promising applications in low-power logic and nonvolatile memories. The ferroelectricity of HfO2 is intrinsically originated from the widely accepted ferroelectric metastable orthorhombic Pca21 phase. In the last decade, defect-doping/solid solution has shown excellent prospects in enhancing and stabilizing the ferroelectricity via isovalent or aliovalent defect-engineering. Here, the recent advances in defect-engineered HfO2-based ferroelectrics are first reviewed, including progress in mono-ionic doping and mixed ion-doping. Then, the defect-lattice correlation, the point-defect promoted phase transition kinetics, and the interface-engineered dynamic behaviour of oxygen vacancy are summarized. In addition, thin film preparation and ion bombardment doping are summarized. Finally, the outlook and challenges are discussed. A multiscale structural optimization approach is suggested for further property optimization. This article not only covers an overview of the state-of-art advances of defects in fluorite ferroelectrics, but also future prospects that may inspire their further property-optimization via defect-engineering.

Magnetic-ferroelectric synergic control of multilevel conducting states in van der Waals multiferroic tunnel junctions towards in-memory computing.

van der Waals (vdW) multiferroic tunnel junctions (MFTJs) based on two-dimensional materials have gained significant interest due to their potential applications in next-generation data storage and in-memory computing devices. In this study, we construct vdW MFTJs by employing monolayer Mn2Se3 as the spin-filter tunnel barrier, TiTe2 as the electrodes and In2S3 as the tunnel barrier to investigate the spin transport properties based on first-principles quantum transport calculations. It is highlighted that apparent tunneling magnetoresistance (TMR) and tunneling electroresistance (TER) effects with a maximum TMR ratio of 6237% and TER ratio of 1771% can be realized by using bilayer In2S3 as the tunnel barrier under finite bias. Furthermore, the physical origin of the distinguished TMR and TER effects is unraveled from the k||-resolved transmission spectra and spin-dependent projected local density of states analysis. Interestingly, four distinguishable conductance states reveal the implementation of four-state nonvolatile data storage using one MFTJ unit. More importantly, in-memory logic computing and multilevel data storage can be achieved at the same time by magnetic switching and electrical control, respectively. These results shed light on vdW MFTJs in the applications of in-memory computing as well as multilevel data storage devices.

Landauer-QFLPS Model for Mixed Schottky-Ohmic Contact Two-Dimensional Transistors.

Two-dimensional material-based field-effect transistors (2DM-FETs) are playing a revolutionary role in electronic devices. However, before electronic design automation (EDA) for 2DM-FETs can be achieved, it remains necessary to determine how to incorporate contact transports into model. Reported methods compromise between physical intelligibility and model compactness due to the heterojunction nature. To address this, quasi-Fermi-level phase space theory (QFLPS) is generalized to incorporate contact transports using the Landauer formula. It turns out that the Landauer-QFLPS model effectively overcomes the issue of concern. The proposed new formula can describe 2DM-FETs with Schottky or Ohmic contacts with superior accuracy and efficiency over previous methods, especially when describing non-monotonic drain conductance characteristics. A three-bit threshold inverter quantizer (TIQ) circuit is fabricated using ambipolar black phosphorus and it is demonstrated that the model accurately predicts circuit performance. The model could be very effective and valuable in the development of 2DM-FET-based integrated circuits.

Self-wavelength shifting in two-dimensional perovskite for sensitive and fast gamma-ray detection.

Lead halide perovskites have recently emerged as promising X/γ-ray scintillators. However, the small Stokes shift of exciton luminescence in perovskite scintillators creates problems for the light extraction efficiency and severely impedes their applications in hard X/γ-ray detection. Dopants have been used to shift the emission wavelength, but the radioluminescence lifetime has also been unwantedly extended. Herein, we demonstrate the intrinsic strain in 2D perovskite crystals as a general phenomenon, which could be utilized as self-wavelength shifting to reduce the self-absorption effect without sacrificing the radiation response speed. Furthermore, we successfully demonstrated the first imaging reconstruction by perovskites for application of positron emission tomography. The coincidence time resolution for the optimized perovskite single crystals (4 × 4 × 0.8 mm3) reached 119 ± 3 ps. This work provides a new paradigm for suppressing the self-absorption effect in scintillators and may facilitate the application of perovskite scintillators in practical hard X/γ-ray detections.

Manipulating exchange bias in 2D magnetic heterojunction for high-performance robust memory applications.

The exchange bias (EB) effect plays an undisputed role in the development of highly sensitive, robust, and high-density spintronic devices in magnetic data storage. However, the weak EB field, low blocking temperature, as well as the lack of modulation methods, seriously limit the application of EB in van der Waals (vdW) spintronic devices. Here, we utilized pressure engineering to tune the vdW spacing of the two-dimensional (2D) FePSe3/Fe3GeTe2 heterostructures. The EB field (HEB, from 29.2 mT to 111.2 mT) and blocking temperature (Tb, from 20 K to 110 K) are significantly enhanced, and a highly sensitive and robust spin valve is demonstrated. Interestingly, this enhancement of the EB effect was extended to exposed Fe3GeTe2, due to the single-domain nature of Fe3GeTe2. Our findings provide opportunities for the producing, exploring, and tuning of magnetic vdW heterostructures with strong interlayer coupling, thereby enabling customized 2D spintronic devices in the future.

On the self-consistency of DFT-1/2.

Density functional theory (DFT)-1/2 is an efficient bandgap rectification method for DFT under local density approximation (LDA) or generalized gradient approximation. It was suggested that non-self-consistent DFT-1/2 should be used for highly ionic insulators like LiF, whereas self-consistent DFT-1/2 should still be used for other compounds. Nevertheless, there is no quantitative criterion prescribed for which implementation should work for an arbitrary insulator, which leads to severe ambiguity in this method. In this work, we analyze the impact of self-consistency in DFT-1/2 and shell DFT-1/2 calculations in insulators or semiconductors with ionic bonds, covalent bonds, and intermediate cases and show that self-consistency is required even for highly ionic insulators for globally better electronic structure details. The self-energy correction renders electrons more localized around the anions in self-consistent LDA-1/2. The well-known delocalization error of LDA is rectified, but with strong overcorrection, due to the presence of additional self-energy potential. However, in non-self-consistent LDA-1/2 calculations, the electron wave functions indicate that such localization is much more severe and beyond a reasonable range because the strong Coulomb repulsion is not counted in the Hamiltonian. Another common drawback of non-self-consistent LDA-1/2 is that the ionicity of the bonding gets substantially enhanced, and the bandgap can be enormously high in mixed ionic-covalent compounds like TiO2.

MOF-Like 3D Graphene-Based Catalytic Membrane Fabricated by One-Step Laser Scribing for Robust Water Purification and Green Energy Production.

Increasing both clean water and green energy demands for survival and development are the grand challenges of our age. Here, we successfully fabricate a novel multifunctional 3D graphene-based catalytic membrane (3D-GCM) with active metal nanoparticles (AMNs) loading for simultaneously obtaining the water purification and clean energy generation, via a "green" one-step laser scribing technology. The as-prepared 3D-GCM shows high porosity and uniform distribution with AMNs, which exhibits high permeated fluxes (over 100 L m-2 h-1) and versatile super-adsorption capacities for the removal of tricky organic pollutants from wastewater under ultra-low pressure-driving (0.1 bar). After adsorption saturating, the AMNs in 3D-GCM actuates the advanced oxidization process to self-clean the fouled membrane via the catalysis, and restores the adsorption capacity well for the next time membrane separation. Most importantly, the 3D-GCM with the welding of laser scribing overcomes the lateral shear force damaging during the long-term separation. Moreover, the 3D-GCM could emit plentiful of hot electrons from AMNs under light irradiation, realizing the membrane catalytic hydrolysis reactions for hydrogen energy generation. This "green" precision manufacturing with laser scribing technology provides a feasible technology to fabricate high-efficient and robust 3D-GCM microreactor in the tricky wastewater purification and sustainable clean energy production as well.

DFT-1/2 and shell DFT-1/2 methods: electronic structure calculation for semiconductors at LDA complexity.

It is known that the Kohn-Sham eigenvalues do not characterize experimental excitation energies directly, and the band gap of a semiconductor is typically underestimated by local density approximation (LDA) of density functional theory (DFT). An embarrassing situation is that one usually uses LDA+Ufor strongly correlated materials with rectified band gaps, but for non-strongly-correlated semiconductors one has to resort to expensive methods like hybrid functionals orGW. In spite of the state-of-the-art meta-generalized gradient approximation functionals like TB-mBJ and SCAN, methods with LDA-level complexity to rectify the semiconductor band gaps are in high demand. DFT-1/2 stands as a feasible approach and has been more widely used in recent years. In this work we give a detailed derivation of the Slater half occupation technique, and review the assumptions made by DFT-1/2 in semiconductor band structure calculations. In particular, the self-energy potential approach is verified through mathematical derivations. The aims, features and principles of shell DFT-1/2 for covalent semiconductors are also accounted for in great detail. Other developments of DFT-1/2 including conduction band correction, DFT+A-1/2, empirical formula for the self-energy potential cutoff radius, etc, are further reviewed. The relations of DFT-1/2 to hybrid functional, sX-LDA,GW, self-interaction correction, scissor's operator as well as DFT+Uare explained. Applications, issues and limitations of DFT-1/2 are comprehensively included in this review.

Highly stable halide perovskites for photocatalysis via multi-dimensional structure design and in situ phase transition.

Lead halide perovskite CsPbBr3 quantum dots (QDs) possess several desirable features which enable them to be promising candidates for photocatalysis. However, the instability caused by their inherent liquid-like ionic properties hampers their further development. Herein, this work employs the surficial molecular modification strategy and a multi-dimensional structure design to ease the instability issue. The additive 2-phenylethanamine bromide (PEABr) can serve as a ligand to compensate for stripping the amine ligands and passivate the surficial bromide vacancy defects of CsPbBr3 QDs in photocatalysis. In addition, PEABr acts as a reactant to form 2D and quasi-2D perovskite nanosheets. The addition of a small amount of these nanosheets into QDs can enhance their general stability due to their unique layered structures. Moreover, PEABr can trigger the phase transition of cubic CsPbBr3 into tetragonal CsPb2Br5. The newly formed Z-scheme homologous heterojunctions further improve the catalytic performance. Simulated photocatalytic dynamics reveals that our multi-dimensional structure favors decreasing the reaction barrier energy and then facilitating the photocatalytic reaction. Therefore, the electron consumption rate of our multi-dimensional perovskites doubles that of pristine CsPbBr3 QDs and also has superior long-term stability.

HfOx /AlOy Superlattice-Like Memristive Synapse.

The adjustable conductance of a two-terminal memristor in a crossbar array can facilitate vector-matrix multiplication in one step, making the memristor a promising synapse for efficiently implementing neuromorphic computing. To achieve controllable and gradual switching of multi-level conductance, important for neuromorphic computing, a theoretical design of a superlattice-like (SLL) structure switching layer for the multi-level memristor is proposed and validated, refining the growth of conductive filaments (CFs) and preventing CFs from the abrupt formation and rupture. Ti/(HfOx /AlOy )SLL /TiN memristors are shown with transmission electron microscopy , X-ray photoelectron spectroscopy , and ab initio calculation findings corroborate the SLL structure of HfOx /AlOy film. The optimized SLL memristor achieves outstanding conductance modulation performance with linearly synaptic weight update (nonlinear factor α = 1.06), and the convolutional neural network based on the SLL memristive synapse improves the handwritten digit recognition accuracy to 94.95%. Meanwhile, this improved synaptic device has a fast operating speed (30 ns), a long data retention time (≥ 104 s at 85 â„ƒ), scalability, and CMOS process compatibility. Finally, its physical nature is explored and the CF evolution process is characterized using nudged elastic band calculations and the conduction mechanism fitting. In this work, as an example the HfOx /AlOy SLL memristor provides a design viewpoint and optimization strategy for neuromorphic computing.

Reversible transition between the polar and antipolar phases and its implications for wake-up and fatigue in HfO2-based ferroelectric thin film.

Atomic-resolution Cs-corrected scanning transmission electron microscopy revealed local shifting of two oxygen positions (OI and OII) within the unit cells of a ferroelectric (Hf0.5Zr0.5)O2 thin film. A reversible transition between the polar Pbc21 and antipolar Pbca phases, where the crystal structures of the 180° domain wall of the Pbc21 phase and the unit cell structure of the Pbca phase were identical, was induced by applying appropriate cycling voltages. The critical field strength that determined whether the film would be woken up or fatigued was ~0.8 MV/cm, above or below which wake-up or fatigue was observed, respectively. Repeated cycling with sufficiently high voltages led to development of the interfacial nonpolar P42/nmc phase, which induced fatigue through the depolarizing field effect. The fatigued film could be rejuvenated by applying a slightly higher voltage, indicating that these transitions were reversible. These mechanisms are radically different from those of conventional ferroelectrics.

In Situ Loading of Cu2O Active Sites on Island-like Copper for Efficient Electrochemical Reduction of Nitrate to Ammonia.

Electrochemical nitrate reduction reaction (NO3RR) offers a new pathway for low-temperature green ammonia synthesis. It is widely known that copper and its copper oxide catalysts are selective for NO3RRs, although the role played by their oxidation state in catalysis is not fully understood. Here, we found that in situ electrochemical reduction modulates the oxidation state of copper facilitating in situ loading of Cu2O active sites on island-like copper, and investigated the effect of cuprous oxide on nitrate reduction. We found that the improvement of ammonia yield (Faraday efficiency: 98.28%, selectivity: 96.6%) was closely related to the generation of Cu2O, which exceeded the performance of the state-of-the-art catalysts available today. The presence of a multilayer structure of the material was demonstrated by X-ray photoelectron spectroscopy combined with ion beam sputtering. Using operando Raman spectroscopy, we monitored the reduction process of the catalyst surface oxide species at the applied potential. Density functional theory (DFT) calculations indicated that the stable presence of Cu(I) effectively promotes the conversion of *HNOH to *HNHOH. We optimized the model building for DFT calculations and established relatively more reliable reaction paths, which provided a strong support for a further understanding of the reaction mechanism of NO3RR.

Evolution of the conductive filament system in HfO2-based memristors observed by direct atomic-scale imaging.

The resistive switching effect in memristors typically stems from the formation and rupture of localized conductive filament paths, and HfO2 has been accepted as one of the most promising resistive switching materials. However, the dynamic changes in the resistive switching process, including the composition and structure of conductive filaments, and especially the evolution of conductive filament surroundings, remain controversial in HfO2-based memristors. Here, the conductive filament system in the amorphous HfO2-based memristors with various top electrodes is revealed to be with a quasi-core-shell structure consisting of metallic hexagonal-Hf6O and its crystalline surroundings (monoclinic or tetragonal HfOx). The phase of the HfOx shell varies with the oxygen reservation capability of the top electrode. According to extensive high-resolution transmission electron microscopy observations and ab initio calculations, the phase transition of the conductive filament shell between monoclinic and tetragonal HfO2 is proposed to depend on the comprehensive effects of Joule heat from the conductive filament current and the concentration of oxygen vacancies. The quasi-core-shell conductive filament system with an intrinsic barrier, which prohibits conductive filament oxidation, ensures the extreme scalability of resistive switching memristors. This study renovates the understanding of the conductive filament evolution in HfO2-based memristors and provides potential inspirations to improve oxide memristors for nonvolatile storage-class memory applications.

Ultra-High Performance Amorphous Ga2 O3 Photodetector Arrays for Solar-Blind Imaging.

The growing demand for scalable solar-blind image sensors with remarkable photosensitive properties has stimulated the research on more advanced solar-blind photodetector (SBPD) arrays. In this work, the authors demonstrate ultrahigh-performance metal-semiconductor-metal (MSM) SBPDs based on amorphous (a-) Ga2 O3 via a post-annealing process. The post-annealed MSM a-Ga2 O3 SBPDs exhibit superhigh sensitivity of 733 A/W and high response speed of 18 ms, giving a high gain-bandwidth product over 104 at 5 V. The SBPDs also show ultrahigh photo-to-dark current ratio of 3.9 × 107 . Additionally, the PDs demonstrate super-high specific detectivity of 3.9 × 1016 Jones owing to the extremely low noise down to 3.5 fW Hz-1/2 , suggesting high signal-to-noise ratio. Underlying mechanism for such superior photoelectric properties is revealed by Kelvin probe force microscopy and first principles calculation. Furthermore, for the first time, a large-scale, high-uniformity 32 × 32 image sensor array based on the post-annealed a-Ga2 O3 SBPDs is fabricated. Clear image of target object with high contrast can be obtained thanks to the high sensitivity and uniformity of the array. These results demonstrate the feasibility and practicality of the Ga2 O3 PDs for applications in solar-blind imaging, environmental monitoring, artificial intelligence and machine vision.

2D materials-based homogeneous transistor-memory architecture for neuromorphic hardware.

In neuromorphic hardware, peripheral circuits and memories based on heterogeneous devices are generally physically separated. Thus, exploration of homogeneous devices for these components is key for improving module integration and resistance matching. Inspired by the ferroelectric proximity effect on two-dimensional (2D) materials, we present a tungsten diselenide­on­lithium niobate cascaded architecture as a basic device that functions as a nonlinear transistor, assisting the design of operational amplifiers for analog signal processing (ASP). This device also functions as a nonvolatile memory cell, achieving memory operating (MO) functionality. On the basis of this homogeneous architecture, we also investigated an ASP-MO integrated system for binary classification and the design of ternary content-addressable memory for potential use in neuromorphic hardware.

Lead halide perovskite for efficient optoacoustic conversion and application toward high-resolution ultrasound imaging.

Lead halide perovskites have exhibited excellent performance in solar cells, LEDs and detectors. Thermal properties of perovskites, such as heat capacity and thermal conductivity, have rarely been studied and corresponding devices have barely been explored. Considering the high absorption coefficient (104~105 cm-1), low specific heat capacity (296-326 J kg-1 K-1) and small thermal diffusion coefficient (0.145 mm2 s-1), herein we showcase the successful use of perovskite in optoacoustic transducers. The theoretically calculated phonon spectrum shows that the overlap of optical phonons and acoustic phonons leads to the up-conversion of acoustic phonons, and thus results in experimentally measured low thermal diffusion coefficient. The assembled device of PDMS/MAPbI3/PDMS simultaneously achieves broad bandwidths (-6 dB bandwidth: 40.8 MHz; central frequency: 29.2 MHz), and high conversion efficiency (2.97 × 10-2), while all these parameters are the record values for optoacoustic transducers. We also fabricate miniatured devices by assembling perovskite film onto fibers, and clearly resolve the fine structure of fisheyes, which demonstrates the strong competitiveness of perovskite based optoacoustic transducers for ultrasound imaging.

Low-Power Memristive Logic Device Enabled by Controllable Oxidation of 2D HfSe2 for In-Memory Computing.

Memristive logic device is a promising unit for beyond von Neumann computing systems and 2D materials are widely used because of their controllable interfacial properties. Most of these 2D memristive devices, however, are made from semiconducting chalcogenides which fail to gate the off-state current. To this end, a crossbar device using 2D HfSe2 is fabricated, and then the top layers are oxidized into "high-k" dielectric HfSex Oy via oxygen plasma treatment, so that the cell resistance can be remarkably increased. This two-terminal Ti/HfSex Oy /HfSe2 /Au device exhibits excellent forming-free resistive switching performance with high switching speed (<50 ns), low operation voltage (<3 V), large switching window (103 ), and good data retention. Most importantly, the operation current and the power consumption reach 100 pA and 0.1 fJ to 0.1 pJ, much lower than other HfO based memristors. A functionally complete low-power Boolean logic is experimentally demonstrated using the memristive device, allowing it in the application of energy-efficient in-memory computing.

Cation and Anion Co-doped Perovskite Nanofibers for Highly Efficient Electrocatalytic Oxygen Evolution.

Perovskite oxides have been recognized as one of the most attractive oxygen evolution reaction (OER) catalysts because of their low cost, earth abundance, and robust nature. Herein, one-dimensional porous LaFe1-xNixO3 (LFNO) perovskite oxide nanofibers (LFNO NFs) are fabricated with a feasible electrospinning route and its further post-calcination treatment. By tailoring the atomic percent of Fe and Ni in the perovskite oxide, we determined that LaFe0.25Ni0.75O3 (LFNO-III) NFs afford the best OER activity among all the prepared perovskite oxides. Especially remarkable is that the further selenide-doped LaFe0.25Ni0.75O3 (LFNOSe-III) NFs exhibit outstanding OER activity with a low overpotential of 287 mV at 10 mA cm-2 and a small Tafel slope of 87 mV dec-1 in 1 M KOH solution, markedly exceeding that of the parent perovskite oxide and the commercial RuO2. It also delivers decent durability with no significant degradation after 22 h of stability test. In the meanwhile, density functional theory calculations are also conducted to justify the optimized adsorption features of *OH, *O, and *OOH intermediates and unveil that the electrocatalytic active sites are the Ni atoms adjacent to Fe in the Ni- and Se codoped perovskite. This work provides an effective method for the development of highly efficient perovskite oxide catalysts.

A new family of two-dimensional ferroelastic semiconductors with negative Poisson's ratios.

Two-dimensional (2D) materials with both ferroelasticity and negative Poisson's ratios have attracted intensive interest, but it is very rare to have both ferroelasticity and negative Poisson's ratios in a single material. Directional positive and negative Poisson's ratios in a switchable ferroelastic dielectric may enable non-destructive readout in ferroelastic data storage. Herein, we propose 14 kinds of stable 2D semiconductors: AB monolayers (A = Sc, Y, La; B = N, P, As, Sb, Bi) based on first-principles calculations. The band gaps of AB monolayers cover a wide range from 0.69 eV to 2.15 eV. Mechanical analysis reveals that these materials are flexible and 12 of 14 are predicted to possess an in-plane negative Poisson's ratio (NPR). Moreover, 10 of these 14 systems possess an out-of-plane NPR. More encouragingly, all AB monolayers are identified as 2D ferroelastic materials with reversible strains of around 5.94% to 20.30%. The ferroelastic switching barriers, mechanical properties and electronic structures of these materials are discussed in detail. Such outstanding properties make the AB monolayers very promising as switchable anisotropic 2D materials for nanoelectronics and micromechanical applications.