Enhanced Oxygen Evolution Electrocatalysis in Strained A-Site Cation Deficient LaNiO3 Perovskite Thin Films.

As the BO6 octahedral structure in perovskite oxide is strongly linked with electronic behavior, it is actively studied for various fields such as metal-insulator transition, superconductivity, and so on. However, the research about the relationship between water-splitting activity and BO6 structure is largely lacking. Here, we report the oxygen evolution reaction (OER) of LaNiO3 (LNO) by changing the NiO6 structure using compositional change and strain. The 5 atom % La deficiency in LNO resulted in an increase of the Ni-O-Ni bond angle and an expansion of bandwidth, enhancing the charge transfer ability. In-plane compressive strain derives the higher dz2 orbital occupancy, leading to suitable metal-oxygen bond strength for OER. Because of the synergistic effect of A-site deficiency and compressive strain, the overpotential (η) of compressively strained L0.95NO film is reduced to 130 mV at j = 30 µA/cm2 compared with nonstrained LNO (η = 280 mV), indicating a significant enhancement in OER.

Lead-Free Dual-Phase Halide Perovskites for Preconditioned Conducting-Bridge Memory.

Organometallic and all-inorganic halide perovskites (HPs) have recently emerged as promising candidate materials for resistive switching (RS) nonvolatile memory due to their current-voltage hysteresis caused by fast ion migration. Lead-free and all-inorganic HPs have been researched for non-toxic and environmentally friendly RS memory devices. However, only HP-based devices with electrochemically active top electrode (TE) exhibit ultra-low operating voltages and high on/off ratio RS properties. The active TE easily reacts to halide ions in HP films, and the devices have a low device durability. Herein, RS memory devices based on an air-stable lead-free all-inorganic dual-phase HP (AgBi2 I7 -Cs3 Bi2 I9 ) are successfully fabricated with inert metal electrodes. The devices with Au TE show filamentary RS behavior by conducting-bridge involving Ag cations in HPs with ultra-low operating voltages (<0.15 V), high on/off ratio (>107 ), multilevel data storage, and long retention times (>5 × 104 s). The use of a closed-loop pulse switching method improves reversible RS properties up to 103 cycles with high on/off ratio above 106 . With an extremely small bending radius of 1 mm, the devices are operable with reasonable RS characteristics. This work provides a promising material strategy for lead-free all-inorganic HP-based nonvolatile memory devices for practical applications.

Nanoelectronics Using Metal-Insulator Transition.

Metal-insulator transition (MIT) coupled with an ultrafast, significant, and reversible resistive change in Mott insulators has attracted tremendous interest for investigation into next-generation electronic and optoelectronic devices, as well as a fundamental understanding of condensed matter systems. Although the mechanism of MIT in Mott insulators is still controversial, great efforts have been made to understand and modulate MIT behavior for various electronic and optoelectronic applications. In this review, recent progress in the field of nanoelectronics utilizing MIT is highlighted. A brief introduction to the physics of MIT and its underlying mechanisms is begun. After discussing the MIT behaviors of various Mott insulators, recent advances in the design and fabrication of nanoelectronics devices based on MIT, including memories, gas sensors, photodetectors, logic circuits, and artificial neural networks are described. Finally, an outlook on the development and future applications of nanoelectronics utilizing MIT is provided. This review can serve as an overview and a comprehensive understanding of the design of MIT-based nanoelectronics for future electronic and optoelectronic devices.

Text Mining the Literature to Inform Experiments and Rationalize Impurity Phase Formation for BiFeO3.

We used data-driven methods to understand the formation of impurity phases in BiFeO3 thin-film synthesis through the sol-gel technique. Using a high-quality dataset of 331 synthesis procedures and outcomes extracted manually from 177 scientific articles, we trained decision tree models that reinforce important experimental heuristics for the avoidance of phase impurities but ultimately show limited predictive capability. We find that several important synthesis features, identified by our model, are often not reported in the literature. To test our ability to correctly impute missing synthesis parameters, we attempted to reproduce nine syntheses from the literature with varying degrees of "missingness". We demonstrate how a text-mined dataset can be made useful by informing new controlled experiments and forming a better understanding for impurity phase formation in this complex oxide system.

Structurally engineered highly efficient electrocatalytic performance of 3-dimensional Mo/Ni chalcogenides for boosting overall water splitting performance.

Hydrogen production from water splitting combined with renewable electricity can provide a viable solution to the energy crisis. A novel MoS2/NiS2/Ni3S4 heterostructure is designed as a bifunctional electrocatalyst by facile hydrothermal method to demonstrate excellent electrocatalytic performance towards overall water splitting applications. MoS2/NiS2/Ni3S4 heterostructure necessitates a low overpotential of 81 mV and 210 mV to attain a current density of 10 mA cm-2 during the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Consequently, the MoS2/NiS2/Ni3S4 heterostructure-based electrolyzer shows a low cell voltage of 1.54 V at 10 mA cm-2. The present work highlights the significance of the heterostructure configuration of transition metal sulfide-based electrocatalysts for electrochemical overall water splitting applications.

Defect engineered ternary metal spinel-type Ni-Fe-Co oxide as bifunctional electrocatalyst for overall electrochemical water splitting.

Transition metal spinel oxides were engineered with active elements as bifunctional water splitting electrocatalysts to deliver superior intrinsic activity, stability, and improved conductivity to support green hydrogen production. In this study, we reported the ternary metal Ni-Fe-Co spinel oxide electrocatalysts prepared by defect engineering strategy with rich and deficient Na+ ions, termed NFCO-Na and NFCO, which suggest the formation of defects with Na+ forming tensile strain. The Na-rich NiFeCoO4 spinel oxide reveals lattice expansion, resulting in the formation of a defective crystal structure, suggesting higher electrocatalytic active sites. The spherical NFCO-Na electrocatalysts exhibit lower OER and HER overpotentials of 248 mV and 153 mV at 10 mA cm-2 and smaller Tafel slope values of about 78 mV dec-1 and 129 mV dec-1, respectively. Notably, the bifunctional NFCO-Na electrocatalyst requires a minimum cell voltage of about 1.67 V to drive a current density of 10 mA cm-2. The present work highlights the significant electrochemical activity of defect-engineered ternary metal oxides, which can be further upgraded as highly active electrocatalysts for water splitting applications.

Memristive Devices Based on Two-Dimensional Transition Metal Chalcogenides for Neuromorphic Computing.

Two-dimensional (2D) transition metal chalcogenides (TMC) and their heterostructures are appealing as building blocks in a wide range of electronic and optoelectronic devices, particularly futuristic memristive and synaptic devices for brain-inspired neuromorphic computing systems. The distinct properties such as high durability, electrical and optical tunability, clean surface, flexibility, and LEGO-staking capability enable simple fabrication with high integration density, energy-efficient operation, and high scalability. This review provides a thorough examination of high-performance memristors based on 2D TMCs for neuromorphic computing applications, including the promise of 2D TMC materials and heterostructures, as well as the state-of-the-art demonstration of memristive devices. The challenges and future prospects for the development of these emerging materials and devices are also discussed. The purpose of this review is to provide an outlook on the fabrication and characterization of neuromorphic memristors based on 2D TMCs.

Architecture engineering of nanostructured catalyst via layer-by-layer adornment of multiple nanocatalysts on silica nanorod arrays for hydrogenation of nitroarenes.

Direct consideration for both, the catalytically active species and the host materials provides highly efficient strategies for the architecture design of nanostructured catalysts. The conventional wet chemical methods have limitations in achieving such unique layer-by-layer design possessing one body framework with many catalyst parts. Herein, an innovative physical method is presented that allows the well-regulated architecture design for an array of functional nanocatalysts as exemplified by layer-by-layer adornment of Pd nanoparticles (NPs) on the highly arrayed silica nanorods. This spatially confined catalyst exhibits excellent efficiency for the hydrogenation of nitroarenes and widely deployed Suzuki cross-coupling reactions; their facile separation from the reaction mixtures is easily accomplished due to the monolithic structure. The generality of this method for the introduction of other metal source has also been demonstrated with Au NPs. This pioneering effort highlights the feasibility of physically controlled architecture design of nanostructured catalysts which may stimulate further studies in the general domain of the heterogeneous catalytic transformations.

One-Step Thermal Gradient- and Antisolvent-Free Crystallization of All-Inorganic Perovskites for Highly Efficient and Thermally Stable Solar Cells.

All-inorganic perovskites have emerged as promising photovoltaic materials due to their superior thermal stability compared to their heat-sensitive hybrid organic-inorganic counterparts. In particular, CsPbI2 Br shows the highest potential for developing thermally-stable perovskite solar cells (PSCs) among all-inorganic compositions. However, controlling the crystallinity and morphology of all-inorganic compositions is a significant challenge. Here, a simple, thermal gradient- and antisolvent-free method is reported to control the crystallization of CsPbI2 Br films. Optical in situ characterization is used to investigate the dynamic film formation during spin-coating and annealing to understand and optimize the evolving film properties. This leads to high-quality perovskite films with micrometer-scale grain sizes with a noteworthy performance of 17% (≈16% stabilized), fill factor (FF) of 80.5%, and open-circuit voltage (VOC ) of 1.27 V. Moreover, excellent phase and thermal stability are demonstrated even after extreme thermal stressing at 300 °C.

Nonvolatile Control of Metal-Insulator Transition in VO2 by Ferroelectric Gating.

Controlling phase transitions in correlated materials yields emergent functional properties, providing new aspects to future electronics and a fundamental understanding of condensed matter systems. With vanadium dioxide (VO2 ), a representative correlated material, an approach to control a metal-insulator transition (MIT) behavior is developed by employing a heteroepitaxial structure with a ferroelectric BiFeO3 (BFO) layer to modulate the interaction of correlated electrons. Owing to the defect-alleviated interfaces, the enhanced coupling between the correlated electrons and ferroelectric polarization is successfully demonstrated by showing a nonvolatile control of MIT of VO2 at room temperature. The ferroelectrically-tunable MIT can be realized through the Mott transistor (VO2 /BFO/SrRuO3 ) with a remanent polarization of 80 µC cm-2 , leading to a nonvolatile MIT behavior through the reversible electrical conductance with a large on/off ratio (≈102 ), long retention time (≈104 s), and high endurance (≈103 cycles). Furthermore, the structural phase transition of VO2 is corroborated by ferroelectric polarization through in situ Raman mapping analysis. This study provides novel design principles for heteroepitaxial correlated materials and innovative insight to modulate multifunctional properties.

SnS2 Nanograins on Porous SiO2 Nanorods Template for Highly Sensitive NO2 Sensor at Room Temperature with Excellent Recovery.

In order to develop high performance chemoresistive gas sensors for Internet of Everything applications, low power consumption should be achieved due to the limited battery capacity of portable devices. One of the most efficient ways to reduce power consumption is to lower the operating temperature to room temperature. Herein, we report superior gas sensing properties of SnS2 nanograins on SiO2 nanorods toward NO2 at room temperature. The gas response is as high as 701% for 10 ppm of NO2 with excellent recovery characteristics and the theoretical detection limit is evaluated to be 408.9 ppb at room temperature, which has not been reported for SnS2-based gas sensors to the best of our knowledge. The SnS2 nanograins on the template used in this study have excessive sulfur component (Sn:S = 1:2.33) and exhibit p-type conduction behavior. These results will provide a new perspective of nanostructured two-dimensional materials for gas sensor applications on demand.

Lead-Free All-Inorganic Cesium Tin Iodide Perovskite for Filamentary and Interface-Type Resistive Switching toward Environment-Friendly and Temperature-Tolerant Nonvolatile Memories.

Recently, organometallic and all-inorganic halide perovskites (HPs) have become promising materials for resistive switching (RS) nonvolatile memory devices with low power consumption because they show current-voltage hysteresis caused by fast ion migration. However, the toxicity and environmental pollution potential of lead, a common constituent of HPs, has limited the commercial applications of HP-based devices. Here, RS memory devices based on lead-free all-inorganic cesium tin iodide (CsSnI3) perovskites with temperature tolerance are successfully fabricated. The devices exhibit reproducible and reliable bipolar RS characteristics in both Ag and Au top electrodes (TEs) with different switching mechanisms. The Ag TE devices show filamentary RS behavior with ultralow operating voltages (<0.15 V). In contrast, the Au TE devices have interface-type RS behavior with gradual resistance changes. This suggests that the RS characteristics are attributed to either the formation of metal filaments or the ion migration of defects in HPs under applied electric fields. These distinct mechanisms may permit the opportunity to design devices for specific purposes. This work will pave the way for lead-free all-inorganic HP-based nonvolatile memory for commercial application in HP-based devices.

Organic-Inorganic Hybrid Halide Perovskites for Memories, Transistors, and Artificial Synapses.

Fascinating characteristics of halide perovskites (HPs), which cannot be seen in conventional semiconductors and metal oxides, have boosted the application of HPs in electronic devices beyond optoelectronics such as solar cells, photodetectors, and light-emitting diodes. Here, recent advances in HP-based memory and logic devices such as resistive-switching memories (i.e., resistive random access memory (RRAM) or memristors), transistors, and artificial synapses are reviewed, focusing on inherently exotic properties of HPs: i) tunable bandgap, ii) facile majority carrier control, iii) fast ion migration, and iv) superflexibility. Various fabrication techniques of HP thin films from solution-based methods to vacuum processes are introduced. Up-to-date work in the field, emphasizing the compositional flexibility of HPs, suggest that HPs are promising candidates for next-generation electronic devices. Taking advantages of their unique electrical properties, low-cost and low-temperature synthesis, and compositional and mechanical flexibility, HPs have enormous potential to provide a new platform for future electronic devices and explosively intensive studies will pave the way in finding new HP materials beyond conventional silicon-based semiconductors to keep up with "More-than-Moore" times.

Synthesis of Numerous Edge Sites in MoS2 via SiO2 Nanorods Platform for Highly Sensitive Gas Sensor.

The utilization of edge sites in two-dimensional materials including transition-metal dichalcogenides (TMDs) is an effective strategy to realize high-performance gas sensors because of their high catalytic activity. Herein, we demonstrate a facile strategy to synthesize the numerous edge sites of vertically aligned MoS2 and larger surface area via SiO2 nanorod (NRs) platforms for highly sensitive NO2 gas sensor. The SiO2 NRs encapsulated by MoS2 film with numerous edge sites and partially vertical-aligned regions synthesized using simple thermolysis process of [(NH4)2MoS4]. Especially, the vertically aligned MoS2 prepared on 500 nm thick SiO2 NRs (500MoS2) shows approximately 90 times higher gas-sensing response to 50 ppm NO2 at room temperature than the MoS2 film prepared on flat SiO2, and the theoretical detection limit is as low as ∼2.3 ppb. Additionally, it shows reliable operation with reversible response to NO2 gas without degradation at an operating temperature of 100 °C. The use of the proposed facile approach to synthesize vertically aligned TMDs using nanostructured platform can be extended for various TMD-based devices including sensors, water splitting catalysts, and batteries.

Enhanced Endurance Organolead Halide Perovskite Resistive Switching Memories Operable under an Extremely Low Bending Radius.

It was demonstrated that organolead halide perovskites (OHPs) show a resistive switching behavior with an ultralow electric field of a few kilovolts per centimeter. However, a slow switching time and relatively short endurance remain major obstacles for the realization of the next-generation memory. Here, we report a performance-enhanced OHP resistive switching device. To fabricate topologically and electronically improved OHP thin films, we added hydroiodic acid solution (for an additive) in the precursor solution of the OHP. With drastically improved morphology such as small grain size, low peak-to-valley depth, and precise thickness, the OHP thin films showed an excellent performance as insulating layers in Ag/CH3NH3PbI3/Pt cells, with an endurance of over 103 cycles, a high on/off ratio of 106, and an operation speed of 640 µs and without electroforming. We suggest plausible resistive switching and conduction mechanisms with current-voltage characteristics measured at various temperatures and with different top electrodes and device structures. Beyond the extended endurance, highly flexible resistive switching devices with a minimum bending radius of 5 mm create opportunities for use in flexible and wearable electronic devices.

Toward High-Performance Hematite Nanotube Photoanodes: Charge-Transfer Engineering at Heterointerfaces.

Vertically ordered hematite nanotubes are considered to be promising photoactive materials for high-performance water-splitting photoanodes. However, the synthesis of hematite nanotubes directly on conducting substrates such as fluorine-doped tin oxide (FTO)/glass is difficult to be achieved because of the poor adhesion between hematite nanotubes and FTO/glass. Here, we report the synthesis of hematite nanotubes directly on FTO/glass substrate and high-performance photoelectrochemical properties of the nanotubes with NiFe cocatalysts. The hematite nanotubes are synthesized by a simple electrochemical anodization method. The adhesion of the hematite nanotubes to the FTO/glass substrate is drastically improved by dipping them in nonpolar cyclohexane prior to postannealing. Bare hematite nanotubes show a photocurrent density of 1.3 mA/cm(2) at 1.23 V vs a reversible hydrogen electrode, while hematite nanotubes with electrodeposited NiFe cocatalysts exhibit 2.1 mA/cm(2) at 1.23 V which is the highest photocurrent density reported for hematite nanotubes-based photoanodes for solar water splitting. Our work provides an efficient platform to obtain high-performance water-splitting photoanodes utilizing earth-abundant hematite and noble-metal-free cocatalysts.

Organolead Halide Perovskites for Low Operating Voltage Multilevel Resistive Switching.

Organolead halide perovskites are used for low-operating-voltage multilevel resistive switching. Ag/CH3 NH3 PbI3 /Pt cells exhibit electroforming-free resistive switching at an electric field of 3.25 × 10(3) V cm(-1) for four distinguishable ON-state resistance levels. The migration of iodine interstitials and vacancies with low activation energies is responsible for the low-electric-field resistive switching via filament formation and annihilation.