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 .

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.

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.

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.

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.

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.

Electronic properties of free-standing TiO2 nanotube arrays fabricated by electrochemical anodization.

Nanotubular TiO2 has attracted considerable attention owing to its unique functional properties, including high surface area and vectorial charge transport along the nanotube, making it a good photocatalytic material. Anodic TiO2-nanotube (TiNT) arrays on a Ti foil substrate were prepared by electrochemical anodic oxidation and SEM/HRTEM/XRD analyses have suggested that the walls of TiO2 tubes are formed from stacked [101] planes (anatase). Both HRTEM and XRD indicate an interplanar spacing of d101 = 0.36 nm in the wall structure. Despite the large amount of work done on nanotube synthesis, a thorough investigation of the electronic and atomic structures of free-standing TiNT arrays has not yet been carried out. X-ray absorption spectroscopy (XAS), resonant inelastic X-ray scattering (RIXS) and scanning photoelectron microscopy (SPEM) are employed herein to examine the electronic and atomic structures at the top and bottom of TiNT arrays. These analyses demonstrate the presence of mixed valence states of the Ti ions (Ti(3+) and Ti(4+)) and a structural distortion at the bottom cap region of the TiNT. Additionally, the results obtained herein suggest the formation of a defective anatase phase at the bottom cap barrier layer between the Ti foil substrate and TiNT during the growth of electrochemically anodized nanotubes.

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.

Surface-enhanced Raman scattering of graphene with photo-assisted-synthesized gold nanoparticles.

This paper presents a convenient and reliable method to prepare gold nanoparticles (AuNPs) on graphene. Photo-assisted synthesis (PAS) was employed to grow AuNPs in AuCl(4)(-) electrolyte on graphene. The size of AuNPs could be as large as 130 nm. This optical method had a steady growth rate of AuNPs. The distribution of AuNPs was well controlled by focusing the laser for PAS. The minimum diameter of the distribution was approximately 1 µm. Surface-enhanced Raman scattering of graphene due to AuNPs was observed. Electrical fields near AuNPs calculated by the finite-difference time-domain algorithm ensured that the Raman enhancement was attributed to the localized surface plasmons of AuNPs.

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.

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.

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.

Interaction between Red Yeast Rice and CYP450 Enzymes/P-Glycoprotein and Its Implication for the Clinical Pharmacokinetics of Lovastatin.

Red yeast rice (RYR) can reduce cholesterol through its active component, lovastatin. This study was to investigate the pharmacokinetic properties of lovastatin in RYR products and potential RYR-drug interactions. Extracts of three registered RYR products (LipoCol Forte, Cholestin, and Xuezhikang) were more effective than pure lovastatin in inhibiting the activities of cytochrome P450 enzymes and P-glycoprotein. Among CYP450 enzymes, RYR showed the highest inhibition on CYP1A2 and CYP2C19, with comparable inhibitory potencies to the corresponding typical inhibitors. In healthy volunteers taking the RYR product LipoCol Forte, the pharmacokinetic properties of lovastatin and lovastatin acid were linear in the dose range of 1 to 4 capsules taken as a single dose and no significant accumulation was observed after multiple dosing. Concomitant use of one LipoCol Forte capsule with nifedipine did not change the pharmacokinetics of nifedipine. Yet, concomitant use of gemfibrozil with LipoCol Forte resulted in a significant increase in the plasma concentration of lovastatin acid. These findings suggest that the use of RYR products may not have effects on the pharmacokinetics of concomitant comedications despite their effects to inhibit the activities of CYP450 enzymes and P-gp, whereas gemfibrozil affects the pharmacokinetics of lovastatin acid when used concomitantly with RYR products.

Differential inhibitory effects of proton pump inhibitors on the metabolism and antiplatelet activities of clopidogrel and prasugrel.

The interaction between proton pump inhibitors (PPIs) and clopidogrel/prasugrel was investigated. The IC50 values of omeprazole, esomeprazole, lansoprazole, pantoprazole and rabeprazole on the metabolic ratios of 2-oxo-clopidogrel/clopidogrel, H4 (the active metabolite of clopidogrel)/2-oxo-clopidogrel and R-138727 (the active metabolite of prasugrel)/prasugrel thiolactone in human liver microsomes were determined. The antiplatelet activities of clopidogrel and prasugrel were measured with or without PPIs. As a result, most PPIs (except for pantoprazole) inhibited the formation of 2-oxo-clopidogrel with IC50 values of 20-32 µm and inhibited the formation of H4 with IC50 values of 6-20 µm. PPIs inhibited the formation of R-138727 with IC50 values of 9-25 µm. Among the tested PPIs, omeprazole exhibited the highest inhibitory potency on the formation of H4. Omeprazole, esomeprazole and rabeprazole exhibited the highest inhibitory potencies on the formation of R-138727. For platelet aggregation, omeprazole and lansoprazole show higher inhibitory effects on the antiplatelet activity of clopidogrel. On the other hand, omeprazole, esomeprazole and rabeprazole significantly decreased the antiplatelet activity of prasugrel thiolactone. These data indicate that PPIs differ in their effects of inhibiting the metabolism and antiplatelet activities of clopidogrel and prasugrel.

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.

Synchrotron scanning photoemission microscopy of homogeneous and heterogeneous metal sulfide minerals.

Scanning photoemission microscopy (SPEM) has been applied to the investigation of homogeneous and heterogeneous metal sulfide mineral surfaces. Three mineral samples were investigated: homogeneous chalcopyrite, heterogeneous chalcopyrite with bornite, and heterogeneous chalcopyrite with pyrite. Sulfur, copper and iron SPEM images, i.e. surface-selective elemental maps with high spatial resolution acquired using the signal from the S 2p and Cu and Fe 3p photoemission peaks, were obtained for the surfaces after exposure to different oxidation conditions (either exposed to air or oxidized in pH 9 solution), in addition to high-resolution photoemission spectra from individual pixel areas of the images. Investigation of the homogeneous chalcopyrite sample allowed for the identification of step edges using the topography SPEM image, and high-resolution S 2p spectra acquired from the different parts of the sample image revealed a similar rate of surface oxidation from solution exposure for both step edge and a nearby terrace site. SPEM was able to successfully distinguish between chalcopyrite and bornite on the heterogeneous sample containing both minerals, based upon sulfur imaging. The high-resolution S 2p spectra acquired from the two regions highlighted the faster air oxidation of the bornite relative to the chalcopyrite. Differentiation between chalcopyrite and pyrite based upon contrast in SPEM images was not successful, owing to either the poor photoionization cross section of the Cu and Fe 3p electrons or issues with rough fracture of the composite surface. In spite of this, high-resolution S 2p spectra from each mineral phase were successfully obtained using a step-scan approach.

Preparation and characterization of an ordered 1-dodecanethiol monolayer on bare Si(111) surface.

We have grown 1-dodecandthiol (DDT) monolayer on a bare Si(111) surface through ultraviolet-assisted photochemical reaction. The resulting monolayer was investigated by means of water contact angle measurement, synchrotron radiation-based high-resolution X-ray photoelectron spectroscopy, and polarization-dependent near-edge X-ray absorption fine structure spectroscopy. These combined probes for characterization reveal a hydrophobic ambient surface; the DDT was directly attached to Si through a Si-S bond, and the molecules formed an ordered monolayer with an average tilt angle of 57° of the alkyl chains relative to the substrate surface.

Scanning photoemission spectromicroscopic study of 4-nm ultrathin SiO(3.4) protrusions probe-induced on the native SiO(2) layer.

Atomic force microscopy probe-induced large-area ultrathin SiO(x) (x ≡ O/Si content ratio and x > 2) protrusions only a few nanometers high on a SiO(2) layer were characterized by scanning photoemission microscopy (SPEM) and X-ray photoemission spectroscopy (XPS). SPEM images of the large-area ultrathin SiO(x) protrusions directly showed the surface chemical distribution and chemical state specifications. The peak intensity ratios of the XPS spectra of the large-area ultrathin SiO(x) protrusions provided the elemental quantification of the Si 2p core levels and Si oxidation states (such as the Si(4+), Si(3+), Si(2+), and Si(1+) species). The O/Si content ratio (x) was evidently determined by the height of the large-area ultrathin SiO(x) protrusions.