Nonvolatile Modulation of Bi2O2Se/Pb(Zr,Ti)O3 Heteroepitaxy.

The pursuit of high-performance electronic devices has driven the research focus toward 2D semiconductors with high electron mobility and suitable band gaps. Previous studies have demonstrated that quasi-2D Bi2O2Se (BOSe) has remarkable physical properties and is a promising candidate for further exploration. Building upon this foundation, the present work introduces a novel concept for achieving nonvolatile and reversible control of BOSe's electronic properties. The approach involves the epitaxial integration of a ferroelectric PbZr0.2Ti0.8O3 (PZT) layer to modify BOSe's band alignment. Within the BOSe/PZT heteroepitaxy, through two opposite ferroelectric polarization states of the PZT layer, we can tune the Fermi level in the BOSe layer. Consequently, this controlled modulation of the electronic structure provides a pathway to manipulate the electrical properties of the BOSe layer and the corresponding devices.

Ultrafast and Broad-Band Graphene Heterojunction Photodetectors with High Gain.

Graphene possesses an exotic band structure that spans a wide range of important technological wavelength regimes for photodetection, all within a single material. Conventional methods aimed at enhancing detection efficiency often suffer from an extended response time when the light is switched off. The task of achieving ultrafast broad-band photodetection with a high gain remains challenging. Here, we propose a devised architecture that combines graphene with a photosensitizer composed of an alternating strip superstructure of WS2-WSe2. Upon illumination, n+-WS2 and p+-WSe2 strips create alternating electron- and hole-conduction channels in graphene, effectively overcoming the tradeoff between the responsivity and switch time. This configuration allows for achieving a responsivity of 1.7 × 107 mA/W, with an extrinsic response time of 3-4 µs. The inclusion of the superstructure booster enables photodetection across a wide range from the near-ultraviolet to mid-infrared regime and offers a distinctive photogating route for high responsivity and fast temporal response in the pursuit of broad-band detection.

Bicontinuous oxide heteroepitaxy with enhanced photoconductivity.

Self-assembled systems have recently attracted extensive attention because they can display a wide range of phase morphologies in nanocomposites, providing a new arena to explore novel phenomena. Among these morphologies, a bicontinuous structure is highly desirable based on its high interface-to-volume ratio and 3D interconnectivity. A bicontinuous nickel oxide (NiO) and tin dioxide (SnO2) heteroepitaxial nanocomposite is revealed here. By controlling their concentration, we fabricated tuneable self-assembled nanostructures from pillars to bicontinuous structures, as evidenced by TEM-energy-dispersive X-ray spectroscopy with a tortuous compositional distribution. The experimentally observed growth modes are consistent with predictions by first-principles calculations. Phase-field simulations are performed to understand 3D microstructure formation and extract key thermodynamic parameters for predicting microstructure morphologies in SnO2:NiO nanocomposites of other concentrations. Furthermore, we demonstrate significantly enhanced photovoltaic properties in a bicontinuous SnO2:NiO nanocomposite macroscopically and microscopically. This research shows a pathway to developing innovative solar cell and photodetector devices based on self-assembled oxides.

Rational Design on Polymorphous Phase Switching in Molybdenum Diselenide-Based Memristor Assisted by All-Solid-State Reversible Intercalation toward Neuromorphic Application.

In this work, a low-power memristor based on vertically stacked two-dimensional (2D) layered materials, achieved by plasma-assisted vapor reaction, as the switching material, with which the copper and gold metals as electrodes featured by reversible polymorphous phase changes from a conducting 1T-phase to a semiconducting 2H-one once copper cations interacted between vertical lamellar layers and vice versa, was demonstrated. Here, molybdenum diselenide was chosen as the switching material, and the reversible polymorphous phase changes activated by the intercalation of Cu cations were confirmed by pseudo-operando Raman scattering, transmission electron microscopy, and scanning photoelectron microscopy under high and low resistance states, respectively. The switching can be activated at about ±1 V with critical currents less than 10 µA with an on/off ratio approaching 100 after 100 cycles and low power consumption of ∼0.1 microwatt as well as linear weight updates controlled by the amount of intercalation. The work provides alternative feasibility of reversible and all-solid-state metal interactions, which benefits monolithic integrations of 2D materials into operative electronic circuits.

Adaptive Optimization Algorithm for Resetting Techniques in Obstacle-Ridden Environments.

Redirected Walking (RDW) algorithms aim to impose several types of gains on users immersed in Virtual Reality and distort their walking paths in the real world, thus enabling them to explore a larger space. Since collision with physical boundaries is inevitable, a reset strategy needs to be provided to allow users to reset when they hit the boundary. However, most reset strategies are based on simple heuristics by choosing a seemingly suitable solution, which may not perform well in practice. In this article, we propose a novel optimization-based reset algorithm adaptive to different RDW algorithms. Inspired by the approach of finite element analysis, our algorithm splits the boundary of the physical world by a set of endpoints. Each endpoint is assigned a reset vector to represent the optimized reset direction when hitting the boundary. The reset vectors on the edge will be determined by the interpolation between two neighbouring endpoints. We conduct simulation-based experiments for three RDW algorithms with commonly used reset algorithms to compare with. The results demonstrate that the proposed algorithm significantly reduces the number of resets.

Patterning and doping of transition metals in tungsten dichalcogenides.

Substitutional transition metal doping in two-dimensional (2D) layered dichalcogenides is of fundamental importance in manipulating their electrical, excitonic, magnetic, and catalytic properties through the variation of the d-electron population. Yet, most doping strategies are spatially global, with dopants embedded concurrently during the synthesis. Here, we report an area-selective doping scheme for W-based dichalcogenide single layers, in which pre-patterned graphene is used as a reaction mask in the high-temperature substitution of the W sublattice. The chemical inertness of the thin graphene layer can effectively differentiate the spatial doping reaction, allowing for local manipulation of the host 2D materials. Using graphene as a mask is also beneficial in the sense that it also acts as an insertion layer between the contact metal and the doped channel, capable of depinning the Fermi level for low contact resistivity. Tracing doping by means of chalcogen labelling, deliberate Cr embedment is found to become energetically favorable in the presence of chalcogen deficiency, assisting the substitution of the W sublattice in the devised chemical vapor doping scheme. Atomic characterization using scanning transmission electron microscopy (STEM) shows that the dopant concentration is controllable and varies linearly with the reaction time in the current doping approach. Using the same method, other transition metal atoms such as Mo, V, and Fe can also be doped in the patterned area.

Defect-engineered room temperature negative differential resistance in monolayer MoS2 transistors.

The negative differential resistance (NDR) effect has been widely investigated for the development of various electronic devices. Apart from traditional semiconductor-based devices, two-dimensional (2D) transition metal dichalcogenide (TMD)-based field-effect transistors (FETs) have also recently exhibited NDR behavior in several of their heterostructures. However, to observe NDR in the form of monolayer MoS2, theoretical prediction has revealed that the material should be more profoundly affected by sulfur (S) vacancy defects. In this work, monolayer MoS2 FETs with a specific amount of S-vacancy defects are fabricated using three approaches, namely chemical treatment (KOH solution), physical treatment (electron beam bombardment), and as-grown MoS2. Based on systematic studies on the correlation of the S-vacancies with both the device's electron transport characteristics and spectroscopic analysis, the NDR has been clearly observed in the defect-engineered monolayer MoS2 FETs with an S-vacancy (VS) amount of ∼5 ± 0.5%. Consequently, stable NDR behavior can be observed at room temperature, and its peak-to-valley ratio can also be effectively modulated via the gate electric field and light intensity. Through these results, it is envisioned that more electronic applications based on defect-engineered layered TMDs will emerge in the near future.

Operando photoelectron spectroscopy analysis of graphene field-effect transistors.

In this study, operando photoelectron spectroscopy was used to characterize the performance of graphene field-effect transistors under working conditions. By sweeping the back-gate voltages, the carrier concentration of the graphene channel on the 150 nm Si3N4/Si substrate was tuned. From the C1s core level spectra acquired under the application of different gate voltages, the binding energy shifts caused by electric-field effects were obtained and analyzed. Together with the C1s peak shape information and the photoluminescence spectrum of the Si3N4/Si substrate, the presence of local potential across the x-ray beam spot associated with defects and gate leakage current in amorphous Si3N4was identified. The presence of defects in Si3N4/Si substrate could not only screen the partial electric field generated by the back gate but also serve as long-range scattering centers to the carriers, thus affecting charge transport in the graphene channel. Our findings will help further investigate the dielectric/graphene interface properties and accelerate the utilization of graphene in real device applications.

Bandgap Shrinkage and Charge Transfer in 2D Layered SnS2 Doped with V for Photocatalytic Efficiency Improvement.

Effects of electronic and atomic structures of V-doped 2D layered SnS2 are studied using X-ray spectroscopy for the development of photocatalytic/photovoltaic applications. Extended X-ray absorption fine structure measurements at V K-edge reveal the presence of VO and VS bonds which form the intercalation of tetrahedral OVS sites in the van der Waals (vdW) gap of SnS2 layers. X-ray absorption near-edge structure (XANES) reveals not only valence state of V dopant in SnS2 is ≈4+ but also the charge transfer (CT) from V to ligands, supported by V Lα,ß resonant inelastic X-ray scattering. These results suggest V doping produces extra interlayer covalent interactions and additional conducting channels, which increase the electronic conductivity and CT. This gives rapid transport of photo-excited electrons and effective carrier separation in layered SnS2 . Additionally, valence-band photoemission spectra and S K-edge XANES indicate that the density of states near/at valence-band maximum is shifted to lower binding energy in V-doped SnS2 compare to pristine SnS2 and exhibits band gap shrinkage. These findings support first-principles density functional theory calculations of the interstitially tetrahedral OVS site intercalated in the vdW gap, highlighting the CT from V to ligands in V-doped SnS2 .

Multiscale structures and rheology of bisurea-loaded resins for anti-sagging applications.

Four representative bisurea molecules (HDI-BA, MDI-BA, TDI-BA, and IPDI-BA) were synthesized and dispersed simultaneously by reacting benzylamine (BA) with various types of diisocyanates in a polyester/ortho-xylene resin medium to produce bisurea-loaded resins (BLRs) for anti-sagging application with paints and coating materials. These bisurea molecules are symmetric and differ only in the central spacer unit, thereby presenting an ideal and simplest model system to delve into the structure-performance relationship. The multiscale structural features arising from self-assembly in each of the BLRs were scrutinized using the combination of multi-angular dynamic light scattering (DLS), small-angle light/X-ray scattering (SALS/SAXS), rheology, and scanning electron/optical microscopy (SEM/OM) characterization. All four BLRs were revealed to foster micron-sized, mostly sphere-like agglomerates, with distinct hierarchical structures that correlate well with their thixotropic and anti-sagging performances. Three BLRs (HDI-BA, MDI-BA, and TDI-BA) produce similar rod-like packing units (10 × 1 × 1 nm3), with only one exception (IPDI-BA) that produces a spherical packing unit (2 nm in diameter). However, the bulk feature of the agglomeration state, which dictates the thixotropic and anti-sagging properties, cannot be readily foreseen from the chemical structure or elementary packing unit of a bisurea. The present findings, while confirming the importance of optimum molecular design that controls the early-stage self-assembly behavior of a bisurea in resin media, highlight the necessity of resolving detailed (multiscale) structural features in order to establish the full structure-performance relationship imperatively needed for like material systems and applications.

Engineering an Indium Selenide van der Waals Interface for Multilevel Charge Storage.

As the continuous miniaturization of floating-gate transistors approaches a physical limit, new innovations in device architectures, working principles, and device materials are in high demand. This study demonstrated a nonvolatile memory structure with multilevel data storage that features a van der Waals gate architecture made up of a partially oxidized surface layer/indium selenide (InSe) van der Waals interface. The key functionality of this proof-of-concept device is provided through the generation of charge-trapping sites via an indirect oxygen plasma treatment on the InSe surface layer. In contrast to floating-gate nonvolatile memory, these sites have the ability to retain charge without the help of a gate dielectric. Together with the layered structure, the surface layer with charge-trapping sites facilitates continual electrostatic doping in the underlying InSe layers. The van der Waals gating effect is further supported by trapped charge-induced core-level energy shifts and relative work function variations obtained from operando scanning X-ray photoelectron spectroscopy and Kelvin probe microscopy, respectively. On modulating the amount of electric field-induced trapped electrons by the electrostatic gate potential, eight distinct storage states remained over 3000 s. Moreover, the device exhibits a high current switching ratio of 106 within 11 cycles. The demonstrated characteristics suggest that the engineering of an InSe interface has potential applications for nonvolatile memory.

Surfactant-Mediated Growth and Patterning of Atomically Thin Transition Metal Dichalcogenides.

The role of additives in facilitating the growth of conventional semiconducting thin films is well-established. Apparently, their presence is also decisive in the growth of two-dimensional transition metal dichalcogenides (TMDs), yet their role remains ambiguous. In this work, we show that the use of sodium bromide enables synthesis of TMD monolayers via a surfactant-mediated growth mechanism, without introducing liquefaction of metal oxide precursors. We discovered that sodium ions provided by sodium bromide chemically passivate edges of growing molybdenum disulfide crystals, relaxing in-plane strains to suppress 3D islanding and promote monolayer growth. To exploit this growth model, molybdenum disulfide monolayers were directly grown into desired patterns using predeposited sodium bromide as a removable template. The surfactant-mediated growth not only extends the families of metal oxide precursors but also offers a way for lithography-free patterning of TMD monolayers on various surfaces to facilitate fabrication of atomically thin electronic devices.

Layer-Dependent and In-Plane Anisotropic Properties of Low-Temperature Synthesized Few-Layer PdSe2 Single Crystals.

Palladium diselenide (PdSe2), a peculiar noble metal dichalcogenide, has emerged as a new two-dimensional material with high predicted carrier mobility and a widely tunable band gap for device applications. The inherent in-plane anisotropy endowed by the pentagonal structure further renders PdSe2 promising for novel electronic, photonic, and thermoelectric applications. However, the direct synthesis of few-layer PdSe2 is still challenging and rarely reported. Here, we demonstrate that few-layer, single-crystal PdSe2 flakes can be synthesized at a relatively low growth temperature (300 °C) on sapphire substrates using low-pressure chemical vapor deposition (CVD). The well-defined rectangular domain shape and precisely determined layer number of the CVD-grown PdSe2 enable us to investigate their layer-dependent and in-plane anisotropic properties. The experimentally determined layer-dependent band gap shrinkage combined with first-principle calculations suggest that the interlayer interaction is weaker in few-layer PdSe2 in comparison with that in bulk crystals. Field-effect transistors based on the CVD-grown PdSe2 also show performances comparable to those based on exfoliated samples. The low-temperature synthesis method reported here provides a feasible approach to fabricate high-quality few-layer PdSe2 for device applications.

A gate-free monolayer WSe2 pn diode.

Interest in bringing p- and n-type monolayer semiconducting transition metal dichalcogenides (TMD) into contact to form rectifying pn diode has thrived since it is crucial to control the electrical properties in two-dimensional (2D) electronic and optoelectronic devices. Usually this involves vertically stacking different TMDs with pn heterojunction or, laterally manipulating carrier density by gate biasing. Here, by utilizing a locally reversed ferroelectric polarization, we laterally manipulate the carrier density and created a WSe2 pn homojunction on the supporting ferroelectric BiFeO3 substrate. This non-volatile WSe2 pn homojunction is demonstrated with optical and scanning probe methods and scanning photoelectron micro-spectroscopy. A homo-interface is a direct manifestation of our WSe2 pn diode, which can be quantitatively understood as a clear rectifying behavior. The non-volatile confinement of carriers and associated gate-free pn homojunction can be an addition to the 2D electron-photon toolbox and pave the way to develop laterally 2D electronics and photonics.

n-Alkanethiols Directly Grown on a Bare Si(111) Surface: From Disordered to Ordered Transition.

We observed the growth phase transition of n-alkanethiols (AT), CH3(CH2)n-1SH, n = 4-16, directly implanted on a bare Si(111) surface, forming an AT monolayer. These monolayers were characterized with static water-contact angle, high-resolution X-ray photoelectron spectroscopy, near-edge X-ray fine-structure spectroscopy, and grazing-angle reflection absorption Fourier-transform infrared spectroscopy. The integrated spectral results indicated that the implanted n-AT molecules formed a self-oriented and densely packed monolayer through formation of an S-Si bond. With the number of carbons in the alkyl chain at six or more, namely beginning at hexanethiol, the molecular monolayer began to develop an orientation-ordered structure, which is clearly shorter than that for AT monolayers on Au and Ag. This result implies that, with a stronger molecule-substrate interaction, an ordered molecular monolayer can form with a short chain.

Critical Intermediate Structure That Directs the Crystalline Texture and Surface Morphology of Organo-Lead Trihalide Perovskite.

We have identified an often observed yet unresolved intermediate structure in a popular processing with dimethylformamide solutions of lead chloride and methylammonium iodide for perovskite solar cells. With subsecond time-resolved grazing-incidence X-ray scattering and X-ray photoemission spectroscopy, supplemental with ab initio calculation, the resolved intermediate structure (CH3NH3)2PbI2Cl2·CH3NH3I features two-dimensional (2D) perovskite bilayers of zigzagged lead-halide octahedra and sandwiched CH3NH3I layers. Such intermediate structure reveals a hidden correlation between the intermediate phase and the composition of the processing solution. Most importantly, the 2D perovskite lattice of the intermediate phase is largely crystallographically aligned with the [110] planes of the three-dimensional perovskite cubic phase; consequently, with sublimation of Cl ions from the organo-lead octahedral terminal corners in prolonged annealing, the zigzagged octahedral layers of the intermediate phase can merge with the intercalated methylammonium iodide layers for templated growth of perovskite crystals. Regulated by annealing temperature and the activation energies of the intermediate and perovskite, deduced from analysis of temperature-dependent structural kinetics, the intermediate phase is found to selectively mature first and then melt along the layering direction for epitaxial conversion into perovskite crystals. The unveiled epitaxial conversion under growth kinetics controls might be general for solution-processed and intermediate-templated perovskite formation.

Optical Forging of Graphene into Three-Dimensional Shapes.

Atomically thin materials, such as graphene, are the ultimate building blocks for nanoscale devices. But although their synthesis and handling today are routine, all efforts thus far have been restricted to flat natural geometries, since the means to control their three-dimensional (3D) morphology has remained elusive. Here we show that, just as a blacksmith uses a hammer to forge a metal sheet into 3D shapes, a pulsed laser beam can forge a graphene sheet into controlled 3D shapes in the nanoscale. The forging mechanism is based on laser-induced local expansion of graphene, as confirmed by computer simulations using thin sheet elasticity theory.

Synthesis of Ultrathin Composition Graded Doped Lateral WSe2/WS2 Heterostructures.

Lateral transition-metal dichalcogenide and their heterostructures have attracted substantial attention, but there lacks a simple approach to produce large-scaled optoelectronic devices with graded composition. In particular, the incorporation of substitution and doping into heterostructure formation is rarely reported. Here, we demonstrate growth of a composition graded doped lateral WSe2/WS2 heterostructure by ambient pressure chemical vapor deposition in a single heat cycle. Through Raman and photoluminescence spectroscopy, we demonstrate that the monolayer heterostructure exhibits a clear interface between two domains and a graded composition distribution in each domain. The coexistence of two distinct doping modes, i.e., interstitial and substitutional doping, was verified experimentally. A distinct three-stage growth mechanism consisting of nucleation, epitaxial growth, and substitution was proposed. Electrical transport measurements reveal that this lateral heterostructure has representative characteristics of a photodiodes. The optoelectronic device based on the lateral WSe2/WS2 heterostructure shows improved photodetection performance in terms of a reasonable responsivity and a large photoactive area.

Local oxidation and reduction of graphene.

Micrometer sized oxidation patterns were created in chemical vapor deposition grown graphene through scanning probe lithography (SPL) and then subsequently reduced by irradiation using a focused x-ray beam. Throughout the process, the films were characterized by lateral force microscopy, micro-Raman and micro-x-ray photoelectron spectroscopy. Firstly, the density of grain boundaries was found to be crucial in determining the maximum possible oxygen coverage with SPL. Secondly, the dominant factor in SPL oxidation was found to be the bias voltage. At low voltages, only structural defects are formed on grain boundaries. Above a distinct threshold voltage, oxygen coverage increased rapidly, with the duration of applied voltage affecting the final oxygen coverage. Finally, we found that, independent of initial conditions, types of defects or the amount of SPL oxidation, the same set of coupled rate equations describes the reduction dynamics with the limiting reduction step being C-C â†’ C=C.