Self-propelled bioglass janus nanomotors for dentin hypersensitivity treatment.

Dentin hypersensitivity treatment is not always successful owing to the exfoliation of the blocking layer. Therefore, efficiently delivering a desensitization agent into the dental tubule is critical. Nanomotors are widely used as in vivo drug delivery systems owing to their strong power and good biocompatibility. Herein, we report a kind of self-propelled bioglass Janus nanomotor with a Pt motion unit (nBGs@Pt) for application in dentin hypersensitivity that was prepared via a simple sol-gel method and magnetron sputtering method, with an average size of 290 nm. The Pt layer as the power unit provided the dynamics to deliver the bioglass (desensitization agent). Using hydrogen peroxide as a fuel, the nBGs@Pt could automatically move in different media. In addition, the nBGs@Pt with a mesoporous structure demonstrated good hydroxyapatite formation performance. An in vitro dentin pressure model was used to verify the blocking ability of the nBGs@Pt in dentin tubules. The dynamics of the nBGs@Pt was sufficient to resist the outflow of dentin fluid and movement into the dentin tubules, with a blocking rate of 58.05%. After remineralization, the blocking rate could reach 96.07% and the formation of hydroxyapatite of up to 10 µm or more occurred. It is expected that this study will provide a simple and feasible new strategy for the painless treatment of dentin sensitivity.

Ultrathin All-2D Lateral Diodes Using Top and Bottom Contacted Laterally Spaced Graphene Electrodes to WS2 Semiconductor Monolayers.

The ultrathin nature of two-dimensional (2D) materials opens up opportunities for creating devices that are substantially thinner than using traditional bulk materials. In this article, monolayer 2D materials grown by the chemical vapor deposition method are used to fabricate ultrathin all-2D lateral diodes. We show that placing graphene electrodes below and above the WS2 monolayer, instead of the same side, results in a lateral device with two different Schottky barrier heights. Due to the natural dielectric environment, the bottom graphene layer is wedged between the WS2 and the SiO2 substrate, which has a different doping level than the top graphene layer that is in contact with WS2 and air. The lateral separation of these two graphene electrodes results in a lateral metal-semiconductor-metal junction with two asymmetric barriers but yet retains its ultrathin form of two-layer thickness. The rectification and diode behavior can be exploited in transistors, photodiodes, and light-emitting devices. We show that the device exhibits a rectification ratio up to 90 under a laser power of 1.37 µW at a bias voltage of ±3 V. We demonstrate that both the back-gate voltage and laser illumination can tune the rectification behavior of the device. Furthermore, the device can generate strong red electroluminescence in the WS2 area across the two graphene electrodes under an average flowing current of 2.16 × 10-5 A. This work contributes to the current understanding of the 2D metal-semiconductor heterojunction and offers an idea to obtain all-2D Schottky diodes by retaining the ultrathin device concept.

Large-Scale Uniform-Patterned Arrays of Ultrathin All-2D Vertical Stacked Photodetector Devices.

The key to unlocking the full potential of two-dimensional (2D) materials in ultrathin opto-electronics is their layer-by-layer integration and the ability to produce them on the wafer scale using traditional industry-compatible technology. Here, we demonstrate a novel stacking method for assembling uniform-patterned periodic 2D arrays into vertical-layered heterostructures. The fabricated heterostructure can serve as photodetectors, with graphene electrodes and transition-metal dichalcogenides as the photo-absorber. All 2D materials used are grown into continuous films with only mono- or bilayer thickness. Each layer is prepatterned into a specific shape on a substrate and then transferred to the device substrate with aligned precision. In order to achieve long-range alignment across the wafer, interlocking marker pairs are used to help guide the lateral accuracy and reduce rotational error. We show hundreds of identical devices produced with 2D periodic spacing on a 1 cm × 1 cm SiO2/Si substrate, a fundamental prerequisite for future pixelated detectors. Statistics of the photovoltaic performance of the devices are reported, with values that are comparable to devices made by chemical vapor deposition-grown materials. Our work provides pathways for the large-scale fabrication of ultrathin all-2D opto-electronics that form the basis of the future in 2D-pixelated cameras and displays.

Operational Limits and Failure Mechanisms in All-2D van der Waals Vertical Heterostructure Devices with Long-Lived Persistent Electroluminescence.

Various 2D materials can be assembled into vertical heterostructure stacks that emit strong electroluminescence. However, to date, most work is done using mechanical exfoliated materials, with little insights gained into the operation limits and failure mechanisms due to the limited number of devices produced and the device-to-device variances. However, when using chemical vapor deposition (CVD) grown 2D crystals, it is possible to construct dozens of devices to generate statistics and ensemble insights, providing a viable way toward scalable industrialization of 2D optoelectronics. In particular, the operation lifetime/duration of electroluminescence and subsequent failure mechanisms are poorly understood. Here, we demonstrate that all-2D vertical layered heterostructure (VLH) devices made using CVD-grown materials (Gr:h-BN:WS2:h-BN:Gr) can generate strong red electroluminescence (EL) with continuous operation for more than 2 h in ambient atmospheric conditions under constant bias. Layer-by-layer controlled assembly is used to achieve graphene top and bottom electrodes in a crossbar geometry, with few layered h-BN continuous films as tunnel barriers for direct carrier injection into semiconducting monolayer WS2 single crystals with direct band gap recombination. Tens of the devices were fabricated in a single chip, with strong EL routinely measured under both positive and negative graphene electrode bias. The success rate for EL emission in devices is over 90%. EL starts to be detected at bias values of ∼5 V, with bright red emission located at the crossbar intersection site, with intensity increasing with applied bias. Long-lived persistent EL is demonstrated for more than 2 h without significant degradation of WS2 under high bias conditions of 20 V. In cycling tests, the EL signal peak position and intensity stay almost the same after several ON/OFF cycles with high bias, which proves that our device has good stability and durability when pulsed. Breakdown of the device is shown to occur at a bias value of ∼35 V, whereby current reduces to zero and EL abruptly stops, due to breakdown of the top graphene electrode, associated with local heating accumulation. This study provides a viable way for wafer-scale fabrication of high-performance 2D EL arrays for ultrathin optoelectronic devices and sheds light on the mechanisms of failure and operation limits of EL devices in ambient conditions.

Phase Variations and Layer Epitaxy of 2D PdSe2 Grown on 2D Monolayers by Direct Selenization of Molecular Pd Precursors.

Two-dimensional (2D) materials and van der Waals heterostructures with atomic-scale thickness provide enormous potential for advanced science and technology. However, insufficient knowledge of compatible synthesis impedes wafer-scale production. PdSe2 and Pd2Se3 are two of the noble transition-metal chalcogenides with excellent physical properties that have recently emerged as promising materials for electronics, optoelectronics, catalyst, and sensors. This research presents a feasible approach to synthesize PdSe2 and Pd2Se3 with inherently asymmetric structure on honeycomb lattice 2D monolayer substrates of graphene and MoS2. We directly deposit a molecular transition-metal precursor complex on the surface of the 2D substrates, followed by low-temperature selenization by chemical vapor flow. Parameter control leads to tuning of the material from monolayer nanocrystals with Pd2Se3 phase, to continuous few-layer PdSe2 films. Annular dark-field scanning transmission electron microscopy (ADF-STEM) reveals the structure, phase variations, and heteroepitaxy at the atomic level. PdSe2 with unconventional interlayer stacking shifts appeared as the kinetic product, whereas the bilayer PdSe2 and monolayer Pd2Se3 are the thermodynamic product. The epitaxial alignment of interlayer rotation and translation between the PdSe2 and underlying 2D substrate was also revealed by ADF-STEM. These results offer both nanoscale and atomic-level insights into direct growth of van der Waals heterostructures, as well as an innovative method for 2D synthesis by predetermined nucleation.

Direct Imaging of Individual Molecular Binding to Clean Nanopore Edges in 2D Monolayer MoS2.

We use annular dark-field scanning transmission electron microscopy (ADF-STEM) to study how solution-deposited molecules bind to the edges and surface regions around nanopores in MoS2 monolayers. Nanopores with clean atomically flat edges and controllable mean diameter were generated by time-dependent large-area electron beam exposure during an in situ heating process, ready for subsequent molecular attachment. An organic molecule was designed to have a dithiolane end group that binds to Mo-terminated sites and a ligand structure that incorporates a single transition metal atom (Pt) marker for ADF-STEM detection. Pt atoms were used to track molecular binding around zigzag edges of MoS2 and to predict the orientations and conformations of molecules upon binding. We found that the molecules preferred to reside on the surface of the MoS2, pointing inward when attaching to the edge, rather than dangling out from the edge into free space, which is attributed to van der Waals interactions between the aromatic core of the molecule and the MoS2 basal planes. These results help us understand the way solution-deposited single molecules attach to free-standing edges of 2D crystals and the influence of van der Waals forces in guiding molecular binding.

Direct Laser Patterning and Phase Transformation of 2D PdSe2 Films for On-Demand Device Fabrication.

Heterophase homojunction formation in atomically thin 2D layers is of great importance for next-generation nanoelectronics and optoelectronics applications. Technologically challenging, controllable transformation between the semiconducting and metallic phases of transition metal chalcogenides is of particular importance. Here, we demonstrate that controlled laser irradiation can be used to directly ablate PdSe2 thin films using high power or trigger the local transformation of PdSe2 into a metallic phase PdSe2-x using lower laser power. Such transformations are possible due to the low decomposition temperature of PdSe2 and a variety of stable phases compared to other 2D transition metal dichalcogenides. Scanning transmission electron microscopy is used to reveal the laser-induced Se-deficient phases of PdSe2 material. The process sensitivity to the laser power allows patterning flexibility for resist-free device fabrication. The laser-patterned devices demonstrate that a laser-induced metallic phase PdSe2-x is stable with increased conductivity by a factor of about 20 compared to PdSe2. These findings contribute to the development of nanoscale devices with homojunctions and scalable methods to achieve structural transformations in 2D materials.

Spatially Controlled Fabrication and Mechanisms of Atomically Thin Nanowell Patterns in Bilayer WS2 Using in Situ High Temperature Electron Microscopy.

We show controlled production of atomically thin nanowells in bilayer WS2 using an in situ heating holder combined with a focused electron beam in a scanning transmission electron microscope (STEM). We systematically study the formation and evolvement mechanism involved in removing a single layer of WS2 within a bilayer region with 2 nm accuracy in location and without punching through to the other layer to create a hole. Best results are found when using a high temperature of 800 °C, because it enables thermally activated atomic migration and eliminates the interference from surface carbon contamination. We demonstrate precise control over spatial distributions with 5 nm accuracy of patterning and the width of nanowells adjustable by dose-dependent parameters. The mechanism of removing a monolayer of WS2 within a bilayer region is different than removing equivalent sections in a monolayer film due to the van der Waals interaction of the underlying remaining layer in the bilayer system that stabilizes the excess W atom stoichiometry within the edges of the nanowell structure and facilitates expansion. This study offers insights for the nanoengineering of nanowells in two-dimensional (2D) transitional metal dichalcogenides (TMDs), which could hold potential as selective traps to localize 2D reactions in molecules and ions, underpinning the broader utilization of 2D material membranes.

Photocurrent Direction Control and Increased Photovoltaic Effects in All-2D Ultrathin Vertical Heterostructures Using Asymmetric h-BN Tunneling Barriers.

Two-dimensional (2D) materials are atomically thick and without out-of-plane dangling bonds. As a result, they could break the confinement of lattice matching, and thus can be freely mixed and matched together to construct vertical van der Waals heterostructures. Here, we demonstrated an asymmetrical vertical structure of graphene/hexagonal boron nitride (h-BN)/tungsten disulfide (WS2)/graphene using all chemical vapor deposition grown 2D materials. Three building blocks are utilized in this construction: conductive graphene as a good alternative for the metal electrode due to its tunable Fermi level and ultrathin nature, semiconducting transition-metal dichalcogenides (TMDs) as an ultrathin photoactive material, and insulating h-BNas a tunneling barrier. Such an asymmetrical vertical structure exhibits a much stronger photovoltaic effect than the symmetrical vertical one without h-BN. By changing the sequence of h-BN in the vertical stack, we could even control the electron flow direction. Also, improvement has been further made by increasing the thickness of h-BN. The photovoltaic effect is attributed to different possibilities of excited electrons on TMDs to migrate to top and bottom graphene electrodes, which is caused by potential differences introduced by an insulating h-BN layer. This study shows that h-BN could be effectively used as a tunneling barrier in the asymmetrical vertical heterostructure to improve photovoltaic effect and control the electron flow direction, which is crucial for the design of other 2D vertical heterostructures to meet various needs of electronic and optoelectronic devices.

High Photoresponsivity in Ultrathin 2D Lateral Graphene:WS2:Graphene Photodetectors Using Direct CVD Growth.

We show that reducing the degree of van der Waals overlapping in all 2D ultrathin lateral devices composed of graphene:WS2:graphene leads to significant increase in photodetector responsivity. This is achieved by directly growing WS2 using chemical vapor deposition (CVD) in prepatterned graphene gaps to create epitaxial interfaces. Direct-CVD-grown graphene:WS2:graphene lateral photodetecting transistors exhibit high photoresponsivities reaching 121 A/W under 2.7 × 105 mW/cm2 532 nm illumination, which is around 2 orders of magnitude higher than similar devices made by the layer-by-layer transfer method. The photoresponsivity of our direct-CVD-grown device shows negative correlation with illumination power under different gate voltages, which is different from similar devices made by the transfer method. We show that the high photoresponsivity is due to the lowering of effective Schottky barrier height by improving the contact between graphene and WS2. Furthermore, the direct CVD growth reduces overlapping sections of WS2:Gr and leads to more uniform lateral systems. This approach provides insights into scalable manufacturing of high-quality 2D lateral electronic and optoelectronic devices.

Symmetry-Controlled Reversible Photovoltaic Current Flow in Ultrathin All 2D Vertically Stacked Graphene/MoS2/WS2/Graphene Devices.

Atomically thin vertical heterostructures are promising candidates for optoelectronic applications, especially for flexible and transparent technologies. Here, we show how ultrathin all two-dimensional vertical-stacked type-II heterostructure devices can be assembled using only materials grown by chemical vapor deposition, with graphene (Gr) as top and bottom electrodes and MoS2/WS2 as the active semiconductor layers in the middle. Furthermore, we show that the stack symmetry, which dictates the type-II directionality, is the dominant factor in controlling the photocurrent direction upon light irradiation, whereas in homobilayers, photocurrent direction cannot be easily controlled because the tunnel barrier is determined by the doping levels of the graphene, which appears fixed for top and bottom graphene layers due to their dielectric environments. Therefore, the ability to direct photovoltaic current flow is demonstrated to be only possible using heterobilayers (HBs) and not homobilayers. We study the photovoltaic effects in more than 40 devices, which allows for statistical verification of performance and comparative behavior. The photovoltage in the graphene/transition-metal dichalcogenide-heterobilayer/graphene (Gr/TMD-HB (MoS2/WS2)/Gr) increases up to 10 times that generated in the monolayer TMD devices under the same optical illumination power, due to efficient charge transfer between WS2 and MoS2 and extraction to graphene electrodes. By applying external gate voltages ( Vg), the band alignment can be tuned, which in turn controls the photovoltaic effect in the vertical heterostructures. The tunneling-assisted interlayer charge recombination also plays a significant role in modulating the photovoltaic effect in the Gr/TMD-HB/Gr. These results provide important insights into how layer symmetry in vertical-stacked graphene/TMD/graphene ultrathin optoelectronics can be used to control electron flow directions during photoexcitation and open up opportunities for tandem cell assembly.

High-Performance Two-Dimensional Schottky Diodes Utilizing Chemical Vapour Deposition-Grown Graphene-MoS2 Heterojunctions.

Heterostructures based on two-dimensional (2D) materials have attracted enormous interest as they display unique functionalities and have potential to be applied in next-generation electronics. In this report, we fabricated three types of heterostructures based on chemical vapor deposition-grown graphene and MoS2. A significant rectification was observed in the Au-MoS2-Gr heterojunction, with a rectification ratio over 2 × 104. The rectifying behavior is reproducible among nearly all 44 devices and is attributed to an asymmetrical Schottky barrier at Au-MoS2 and MoS2-graphene contacts. This rectification can be tuned by external gating and laser illumination, which have different impact on the rectifying ratio. This modulation of the Schottky barrier is evidenced by output characteristics of two symmetrical heterostructures: Au-MoS2-Au and Gr-MoS2-Gr field-effect transistors. The effective heights of MoS2-graphene and MoS2-Au Schottky barriers and their response to back-gate voltage and laser irradiation were extracted from output characteristics of Au-MoS2-Au and Gr-MoS2-Gr field-effect transistors. The tuned Schottky barriers could be explained by the Fermi level change of graphene and MoS2. These results contributed to our understanding of 2D heterostructures and have potential applications in novel electronics and optoelectronics.