Engineering covalently bonded 2D layered materials by self-intercalation.

Two-dimensional (2D) materials1-5 offer a unique platform from which to explore the physics of topology and many-body phenomena. New properties can be generated by filling the van der Waals gap of 2D materials with intercalants6,7; however, post-growth intercalation has usually been limited to alkali metals8-10. Here we show that the self-intercalation of native atoms11,12 into bilayer transition metal dichalcogenides during growth generates a class of ultrathin, covalently bonded materials, which we name ic-2D. The stoichiometry of these materials is defined by periodic occupancy patterns of the octahedral vacancy sites in the van der Waals gap, and their properties can be tuned by varying the coverage and the spatial arrangement of the filled sites7,13. By performing growth under high metal chemical potential14,15 we can access a range of tantalum-intercalated TaS(Se)y, including 25% Ta-intercalated Ta9S16, 33.3% Ta-intercalated Ta7S12, 50% Ta-intercalated Ta10S16, 66.7% Ta-intercalated Ta8Se12 (which forms a Kagome lattice) and 100% Ta-intercalated Ta9Se12. Ferromagnetic order was detected in some of these intercalated phases. We also demonstrate that self-intercalated V11S16, In11Se16 and FexTey can be grown under metal-rich conditions. Our work establishes self-intercalation as an approach through which to grow a new class of 2D materials with stoichiometry- or composition-dependent properties.

2D Memory Selectors with Giant Nonlinearity Enabled by Van der Waals Heterostructures.

The integration of one-selector-one-resistor crossbar arrays requires the selectors featured with high nonlinearity and bipolarity to prevent leakage currents and any crosstalk among distinct cells. However, a selector with sufficient nonlinearity especially in the frame of device miniaturization remains scarce, restricting the advance of high-density storage devices. Herein, a high-performance memory selector is reported by constructing a graphene/hBN/WSe2 heterostructure. Within the temperature range of 300-80 K, the nonlinearity of this selector varies from ≈103 - ≈104 under forward bias, and increases from ≈300 - ≈105 under reverse bias, the highest reported nonlinearity among 2D selectors. This improvement is ascribed to direct tunneling at low bias and Fowler-Nordheim tunneling at high bias. The tunneling current versus voltage curves exhibit excellent bipolarity behavior because of the comparable hole and electron tunneling barriers, and the charge transport polarity can be effectively tuned from N-type or P-type to bipolar by simply changing source-drain bias. In addition, the conceptual memory selector exhibits no sign of deterioration after 70 000 switching cycles, paving the way for assembling 2D selectors into modern memory devices.

Silver nanoparticle-induced enhancement of light extraction in two-dimensional light-emitting diodes.

Monolayer transition metal dichalcogenides (TMDCs) with direct bandgaps are considered promising candidates for building light-emitting diodes (LEDs). One crucial indicator of their performance is the brightness of electroluminescence (EL). In this study, we fabricate WS2-based LEDs that make full use of the assistance of effective transient-mode charge injection. By introducing self-assembled silver nanoparticles (NPs) on top of the LED, the extraction efficiency is significantly improved, with a 2.9-fold EL enhancement observed in the experiment. Full-wave simulations further confirm that the improvement comes from the scattering capability of silver NPs, with results qualitatively fitting the experiment. This approach, with its compatibility with van der Waals heterostructures, can be further promoted to enhance the brightness of 2D monolayer TMDC-based LEDs.

Phase Diagram and Superconducting Dome of Infinite-Layer Nd_{1-x}Sr_{x}NiO_{2} Thin Films.

Infinite-layer Nd_{1-x}Sr_{x}NiO_{2} thin films with Sr doping level x from 0.08 to 0.3 are synthesized and investigated. We find a superconducting dome x between 0.12 and 0.235 accompanied by a weakly insulating behavior in both under- and overdoped regimes. The dome is akin to that in the electron-doped 214-type and infinite-layer cuprate superconductors. For x≥0.18, the normal state Hall coefficient (R_{H}) changes the sign from negative to positive as the temperature decreases. The temperature of the sign changes decreases monotonically with decreasing x from the overdoped side and approaches the superconducting dome at the midpoint, suggesting a reconstruction of the Fermi surface with the dopant concentration across the dome.

Photoluminescence Upconversion by Defects in Hexagonal Boron Nitride.

Hexagonal boron nitride (h-BN) was recently reported to display single photon emission from ultraviolet to near-infrared range due to the existence of defects. Single photon emission has potential applications in quantum information processing and optoelectronics. These findings trigger increasing research interests in h-BN defects, such as revealing the nature of the defects. Here, we report another intriguing defect property in h-BN, namely photoluminescence (PL) upconversion (anti-Stokes process). The energy gain by the PL upconversion is about 162 meV. The anomalous PL upconversion is attributed to optical phonon absorption in the one-photon excitation process, based on excitation power, excitation wavelength, and temperature-dependence investigations. Possible constitutions of the defects are discussed from the results of scanning transmission electron microscopy (STEM) studies and theoretical calculations. These findings show that defects in h-BN exhibit strong defect-phonon coupling. The results from STEM and theoretical calculations are beneficial for understanding the constitution of the h-BN defects.

Mo-Terminated Edge Reconstructions in Nanoporous Molybdenum Disulfide Film.

The catalytic and magnetic properties of molybdenum disulfide (MoS2) are significantly enhanced by the presence of edge sites. One way to obtain a high density of edge sites in a two-dimensional (2D) film is by introducing porosity. However, the large-scale bottom-up synthesis of a porous 2D MoS2 film remains challenging and the correlation of growth conditions to the atomic structures of the edges is not well understood. Here, using molecular beam epitaxy, we prepare wafer-scale nanoporous MoS2 films under conditions of high Mo flux and study their catalytic and magnetic properties. Atomic-resolution electron microscopy imaging of the pores reveals two new types of reconstructed Mo-terminated edges, namely, a distorted 1T (DT) edge and the Mo-Klein edge. Nanoporous MoS2 films are magnetic up to 400 K, which is attributed to the presence of Mo-terminated edges with unpaired electrons, as confirmed by density functional theory calculation. The small hydrogen adsorption free energy at these Mo-terminated edges leads to excellent activity for the hydrogen evolution reaction.

Ultrafast Photogenerated Hole Extraction/Transport Behavior in a CH3 NH3 PbI3 /Carbon Nanocomposite and Its Application in a Metal-Electrode-Free Solar Cell.

Aligned and flexible electrospun carbon nanomaterials are used to synthesize carbon/perovskite nanocomposites. The free-electron diffusion length in the CH3 NH3 PbI3 phase of the CH3 NH3 PbI3 /carbon nanocomposite is almost twice that of bare CH3 NH3 PbI3 , and nearly 95 % of the photogenerated free holes can be injected from the CH3 NH3 PbI3 phase into the carbon nanomaterial. The exciton binding energy of the composite is estimated to be 23 meV by utilizing temperature-dependent optical absorption spectroscopy. The calculated free carriers increase with increasing total photoexcitation density, and this broadens the potential of this material for a broad range of optoelectronics applications. A metal-electrode-free perovskite solar cell (power conversion efficiency: 13.0 %) is fabricated with this perovskite/carbon composite, which shows great potential for the fabrication of efficient, large-scale, low-cost, and metal-electrode-free perovskite solar cells.

Van der Waals integrated single-junction light-emitting diodes exceeding 10% quantum efficiency at room temperature.

The construction of miniaturized light-emitting diodes (LEDs) with high external quantum efficiency (EQE) at room temperature remains a challenge for on-chip optoelectronics. Here, we demonstrate microsized LEDs fabricated by a dry-transfer van der Waals (vdW) integration method using typical layered Ruddlesden-Popper perovskites (RPPs). A single-crystalline layered RPP nanoflake is used as the active layer and sandwiched between two few-layer graphene contacts, forming van der Waals LEDs (vdWLEDs). Strong electroluminescence (EL) emission with a low turn-on current density of ~20 pA µm-2 and high EQE exceeding 10% is observed at room temperature, which sets the benchmark for the EQE of vdWLEDs ever recorded. Such efficient EL emission is attributed to the inherent multiple quantum well structure and high photoluminescence quantum yield (~35%) of RPPs and a low charge injection barrier of ~0.10 eV facilitated by the Fowler-Nordheim tunneling mechanism. These findings promise a scalable pathway for accessing high-performance miniaturized light sources for on-chip optical optoelectronics.

Interfacial Effect on the Transient Dielectric Function and Charge Transfer in a Monolayer WS2/Si Heterojunction.

Monolayer tungsten disulfide (WS2) is a highly promising material for silicon photonics. Thus, the WS2/Si interface plays a very important role due to the interfacial complex effects and abundant states. Among them, the effect of charge transfer on exciton dynamics and the optoelectronic property is determined by the dielectric function, which is very crucial for the performance of optoelectronic devices. However, research on the exciton dynamics or the transient dielectric function of WS2 in such WS2/Si junctions is still rare. In this work, both the transient dielectric function and charge transfer of WS2/Si heterojunctions are analyzed based on the transient reflectance spectra measured by the pump-probe spectrometer. The dynamic processes of the A exciton, affected by charge transfer within the WS2/Si heterojunction, are interpreted. Moreover, the transient dielectric function of WS2 is quantitatively analyzed. The dielectric function of WS2 exhibits a notable 19% change, persisting for more than 180 ps within the WS2/Si heterojunction. These findings can pave the way for the advancement of silicon photonic devices based on WS2.

A Time-Division Position-Sensitive Detector Image System for High-Speed Multitarget Trajectory Tracking.

High-speed trajectory tracking with real-time processing capability is particularly important in the fields of pilotless automobiles, guidance systems, robotics, and filmmaking. The conventional optical approach to high-speed trajectory tracking involves charge coupled device (CCD) or complementary metal-oxide-semiconductor (CMOS) image sensors, which suffer from trade-offs between resolution and framerates, complexity of the system, and enormous data-analysis processes. Here, a high-speed trajectory tracking system is designed by using a time-division position-sensitive detector (TD-PSD) based on a graphene-silicon Schottky heterojunction. Benefiting from the high-speed optoelectronic response and sub-micrometer positional accuracy of the TD-PSD, multitarget real-time trajectory tracking is realized, with a maximum image output framerate of up to 62 000 frames per second. Moreover, multichannel trajectory tracking and image-distortion correction functionalities are realized by TD-PSD systems through frequency-related image preprocessing, which significantly improves the capacity of real-time information processing and image quality in complicated light environments.

Multilevel polarization-fields enhanced capture and photocatalytic conversion of particulate matter over flexible schottky-junction nanofiber membranes.

Atmospheric Particulate matter (PM) with small sizes has caused a serious air-pollution problem calling for high-performance PM-capture materials and promising remediation strategies. In this contribution, we propose a new idea to proactively capture PM and simultaneously in-situ convert the captured PM pollution over the flexible schottky-junctions nanofiber membrane (NFM) consisting of rutile TiO2 nanoparticles (NPs)-decorated electrospun carbon NFs. We also demonstrate that both the interfacial electron-transfer process at the TiO2/carbon schottky-junctions and the photo-excitation process at the surface of TiO2 NPs can induce polarization fields in the TiO2/carbon NFM due to the difference of the space-charge distribution. These multilevel polarization fields can drive the long-range electrostatic force to enhance the proactive PM-capture ability of the NFM. As such, the TiO2/carbon NFM exhibited a satisfactory quality factor (0.11 Pa-1) for balancing the PM2.5-filtration efficiency (99.92 %) and the pressure drop (only 63 Pa). More importantly, upon UV-vis-light irradiation, 92.98 % of the ultrafine PM0.3 was removed over this TiO2/carbon NFM. Furthermore, the as-captured PM on the NFM could be photocatalytically decomposed by the photoactive-component of TiO2 NPs, during which some of the carbonaceous PM was converted into the fuels of such CO and CH4 through a multi-step photoreaction.

Electronic and plasmonic phenomena at nonstoichiometric grain boundaries in metallic SrNbO3.

Grain boundaries could exhibit exceptional electronic structure and exotic properties, which are determined by a local atomic configuration and stoichiometry that differs from the bulk. However, optical and plasmonic properties at the grain boundaries in metallic oxides have rarely been discussed before. Here, we show that non-stoichiometric grain boundaries in the newly discovered metallic SrNbO3 photocatalyst show exotic electronic, optical and plasmonic phenomena in comparison to bulk. Aberration-corrected scanning transmission electron microscopy and first-principles calculations reveal that a Nb-rich grain boundary exhibits an increased carrier concentration with quasi-1D metallic conductivity, and newly induced electronic states contributing to the broad energy range of optical absorption. More importantly, dielectric function calculations reveal extended and enhanced plasmonic excitations compared with bulk SrNbO3. Our results show that non-stoichiometric grain boundaries might be utilized to control the electronic and plasmonic properties in oxide photocatalysis.

Atomic scale characterization of point and extended defects in niobate thin films.

Niobium-based oxides have a wide range of applications owing to their rich crystal and electronic structures. Defects at the atomic scale are always unavoidable and will affect their functionalities, especially when in the form of thin films. Here, atomic resolution scanning transmission electron microscopy and electron energy loss spectroscopy have been performed on various defects (point, line, planar defects and segregated phases) in alkaline and alkaline-earth niobate thin films: CaZrO3 modified (K, Na)NbO3 and strontium niobate (SNO), respectively. In CaZrO3 modified (K,Na)NbO3 thin films, a tetragonal tungsten bronze phase was found, with a sharp boundary with the perovskite phase. In SNO thin films, several kinds of point defects and antiphase boundaries are commonly observed. In addition, a strongly Sr deficient phase, SrNb2O6, precipitates inside the SrNbO3 phase with a coherent interface. The different oxidation states of Nb in SrNbO3 and SrNb2O6 were revealed from the O K edge. Our characterization of the point defects and extended defects in niobate thin films offers practical guidelines for thin film deposition or discovery of defect-based novel functionalities.

Electronic-reconstruction-enhanced hydrogen evolution catalysis in oxide polymorphs.

Transition metal oxides exhibit strong structure-property correlations, which has been extensively investigated and utilized for achieving efficient oxygen electrocatalysts. However, high-performance oxide-based electrocatalysts for hydrogen evolution are quite limited, and the mechanism still remains elusive. Here we demonstrate the strong correlations between the electronic structure and hydrogen electrocatalytic activity within a single oxide system Ti2O3. Taking advantage of the epitaxial stabilization, the polymorphism of Ti2O3 is extended by stabilizing bulk-absent polymorphs in the film-form. Electronic reconstructions are realized in the bulk-absent Ti2O3 polymorphs, which are further correlated to their electrocatalytic activity. We identify that smaller charge-transfer energy leads to a substantial enhancement in the electrocatalytic efficiency with stronger hybridization of Ti 3d and O 2p orbitals. Our study highlights the importance of the electronic structures on the hydrogen evolution activity of oxide electrocatalysts, and also provides a strategy to achieve efficient oxide-based hydrogen electrocatalysts by epitaxial stabilization of bulk-absent polymorphs.

Anatase TiO2-A Model System for Large Polaron Transport.

Large polarons have been of significant recent technological interest as they screen and protect electrons from point-scattering centers. Anatase TiO2 is a model system for studying large polarons as they can be studied systematically over a wide range of temperature and carrier density. The electronic and magneto transport properties of reduced anatase TiO2 epitaxial thin films are analyzed considering various polaronic effects. Unexpectedly, with increasing carrier concentration, the mobility increases, which rarely happens in common metallic systems. We find that the screening of the electron-phonon (e-ph) coupling by excess carriers is necessary to explain this unusual dependence. We also find that the magnetoresistance could be decomposed into a linear and a quadratic component, separately characterizing the carrier transport and trapping as a function of temperature, respectively. The various transport behaviors could be organized into a single phase diagram, which clarifies the evolution of large polaron in this material.

The Mechanism of Electrolyte Gating on High-Tc Cuprates: The Role of Oxygen Migration and Electrostatics.

Electrolyte gating is widely used to induce large carrier density modulation on solid surfaces to explore various properties. Most of past works have attributed the charge modulation to electrostatic field effect. However, some recent reports have argued that the electrolyte gating effect in VO2, TiO2, and SrTiO3 originated from field-induced oxygen vacancy formation. This gives rise to a controversy about the gating mechanism, and it is therefore vital to reveal the relationship between the role of electrolyte gating and the intrinsic properties of materials. Here, we report entirely different mechanisms of electrolyte gating on two high-Tc cuprates, NdBa2Cu3O7-δ (NBCO) and Pr2-xCexCuO4 (PCCO), with different crystal structures. We show that field-induced oxygen vacancy formation in CuO chains of NBCO plays the dominant role, while it is mainly an electrostatic field effect in the case of PCCO. The possible reason is that NBCO has mobile oxygen in CuO chains, while PCCO does not. Our study helps clarify the controversy relating to the mechanism of electrolyte gating, leading to a better understanding of the role of oxygen electro migration which is very material specific.

Tunable and low-loss correlated plasmons in Mott-like insulating oxides.

Plasmonics has attracted tremendous interests for its ability to confine light into subwavelength dimensions, creating novel devices with unprecedented functionalities. New plasmonic materials are actively being searched, especially those with tunable plasmons and low loss in the visible-ultraviolet range. Such plasmons commonly occur in metals, but many metals have high plasmonic loss in the optical range, a main issue in current plasmonic research. Here, we discover an anomalous form of tunable correlated plasmons in a Mott-like insulating oxide from the Sr1-xNb1-yO3+δ family. These correlated plasmons have multiple plasmon frequencies and low loss in the visible-ultraviolet range. Supported by theoretical calculations, these plasmons arise from the nanometre-spaced confinement of extra oxygen planes that enhances the unscreened Coulomb interactions among charges. The correlated plasmons are tunable: they diminish as extra oxygen plane density or film thickness decreases. Our results open a path for plasmonics research in previously untapped insulating and strongly-correlated materials.