Substitutional doping of transition metal dichalcogenides (TMDs) may provide routes to achieving tunable p-n junctions, bandgaps, chemical sensitivity, and magnetism in these materials. In this study, we demonstrate in situ doping of monolayer molybdenum disulfide (MoS2) with manganese (Mn) via vapor phase deposition techniques. Successful incorporation of Mn in MoS2 leads to modifications of the band structure as evidenced by photoluminescence and X-ray photoelectron spectroscopy, but this is heavily dependent on the choice of substrate. We show that inert substrates (i.e., graphene) permit the incorporation of several percent Mn in MoS2, while substrates with reactive surface terminations (i.e., SiO2 and sapphire) preclude Mn incorporation and merely lead to defective MoS2. The results presented here demonstrate that tailoring the substrate surface could be the most significant factor in substitutional doping of TMDs with non-TMD elements.
The rise of two-dimensional (2D) materials research took place following the isolation of graphene in 2004. These new 2D materials include transition metal dichalcogenides, mono-elemental 2D sheets, and several carbide-and nitride-based materials. The number of publications related to these emerging materials has been drastically increasing over the last five years. Thus, through this comprehensive review, we aim to discuss the most recent groundbreaking discoveries as well as emerging opportunities and remaining challenges. This review starts out by delving into the improved methods of producing these new 2D materials via controlled exfoliation, metal organic chemical vapor deposition, and wet chemical means. We look into recent studies of doping as well as the optical properties of 2D materials and their heterostructures. Recent advances towards applications of these materials in 2D electronics are also reviewed, and include the tunnel MOSFET and ways to reduce the contact resistance for fabricating highquality devices. Finally, several unique and innovative applications recently explored are discussed as well as perspectives of this exciting and fast moving field.
Atomically thin transition metal dichalcogenides (TMDs) are of interest for next-generation electronics and optoelectronics. Here, we demonstrate device-ready synthetic tungsten diselenide (WSe) via metal-organic chemical vapor deposition and provide key insights into the phenomena that control the properties of large-area, epitaxial TMDs. When epitaxy is achieved, the sapphire surface reconstructs, leading to strong 2D/3D (i.e., TMD/substrate) interactions that impact carrier transport. Furthermore, we demonstrate that substrate step edges are a major source of carrier doping and scattering. Even with 2D/3D coupling, transistors utilizing transfer-free epitaxial WSe/sapphire exhibit ambipolar behavior with excellent on/off ratios (∼10), high current density (1-10 μA·μm), and good field-effect transistor mobility (∼30 cm·V·s) at room temperature. This work establishes that realization of electronic-grade epitaxial TMDs must consider the impact of the TMD precursors, substrate, and the 2D/3D interface as leading factors in electronic performance.
When designing semiconductor heterostructures, it is expected that epitaxial alignment will facilitate low-defect interfaces and efficient vertical transport. Here, we report lattice-matched epitaxial growth of molybdenum disulfide (MoS2) directly on gallium nitride (GaN), resulting in high-quality, unstrained, single-layer MoS2 with strict registry to the GaN lattice. These results present a promising path toward the implementation of high-performance electronic devices based on 2D/3D vertical heterostructures, where each of the 3D and 2D semiconductors is both a template for subsequent epitaxial growth and an active component of the device. The MoS2 monolayer triangles average 1 μm along each side, with monolayer blankets (merged triangles) exhibiting properties similar to that of single-crystal MoS2 sheets. Photoluminescence, Raman, atomic force microscopy, and X-ray photoelectron spectroscopy analyses identified monolayer MoS2 with a prominent 20-fold enhancement of photoluminescence in the center regions of larger triangles. The MoS2/GaN structures are shown to electrically conduct in the out-of-plane direction, confirming the potential of directly synthesized 2D/3D semiconductor heterostructures for vertical current flow. Finally, we estimate a MoS2/GaN contact resistivity to be less than 4 Ω·cm(2) and current spreading in the MoS2 monolayer of approximately 1 μm in diameter.
Since their modern debut in 2004, 2-dimensional (2D) materials continue to exhibit scientific and industrial promise, providing a broad materials platform for scientific investigation, and development of nano-and atomic-scale devices. A significant focus of the last decade's research in this field has been 2D semiconductors, whose electronic properties can be tuned through manipulation of dimensionality, substrate engineering, strain, and doping. 1-8 2D semiconductors such as molybdenum disulfide (MoS2) and tungsten diselenide (WSe2) have dominated recent interest for potential integration in electronic technologies, due to their intrinsic and tunable properties, atomic-scale thicknesses, and relative ease of stacking to create new and custom structures. However, to go "beyond the bench", advances in large-scale, 2D layer synthesis and engineering must lead to "exfoliation-quality" 2D layers at the wafer scale. This roadmap aims to address this grand challenge by identifying key technology drivers where 2D layers can have an impact, and to discuss synthesis and layer engineering for the realization of electronic-grade, 2D materials. We focus on three fundamental areas of research that must be heavily pursued in both experiment and computation to achieve high-quality materials for electronic and optoelectronic applications. The document is organized as follows:
Doping is a fundamental requirement for tuning and improving the properties of conventional semiconductors. Recent doping studies including niobium (Nb) doping of molybdenum disulfide (MoS 2 ) and tungsten (W) doping of molybdenum diselenide (MoSe 2 ) have suggested that substitutional doping may provide an efficient route to tune the doping type and suppress deep trap levels of two dimensional (2D) materials. To date, the impact of the doping on the structural, electronic and photonic properties of in-situ doped monolayers remains unanswered due to challenges This article is protected by copyright. All rights reserved.2 including strong film-substrate charge transfer, and difficulty achieving doping concentrations greater than 0.3 at%. Here, we demonstrate in-situ rhenium (Re) doping of synthetic monolayer MoS 2 with ~1 at% Re. To limit substrate-film charge transfer r-plane sapphire is used. Electronic measurements demonstrate that 1 at% Re doping achieves nearly degenerate n-type doping, which agrees with density functional theory calculations. Moreover, low-temperature photoluminescence (PL) indicates a significant quench of the defect-bound emission when Re is introduced, which is attributed to the Mo-O bond and sulfur vacancies passivation and reduction in gap states due to the presence of Re.The work presented here demonstrates that Re doping of MoS 2 is a promising route towards electronic and photonic engineering of 2D materials.
Vertical stacking of two-dimensional (2D) crystals has recently attracted substantial interest due to unique properties and potential applications they can introduce. However, little is known about their microstructure because fabrication of the 2D heterostructures on a rigid substrate limits one's ability to directly study their atomic and chemical structures using electron microscopy. This study demonstrates a unique approach to create atomically thin freestanding van der Waals heterostructures-WSe2/graphene and MoS2/graphene-as ideal model systems to investigate the nucleation and growth mechanisms in heterostructures. In this study, we use transmission electron microscopy (TEM) imaging and diffraction to show epitaxial growth of the freestanding WSe2/graphene heterostructure, while no epitaxy is maintained in the MoS2/graphene heterostructure. Ultra-high-resolution aberration-corrected scanning transmission electron microscopy (STEM) shows growth of monolayer WSe2 and MoS2 triangles on graphene membranes and reveals their edge morphology and crystallinity. Photoluminescence measurements indicate a significant quenching of the photoluminescence response for the transition metal dichalcogenides on freestanding graphene, compared to those on a rigid substrate, such as sapphire and epitaxial graphene. Using a combination of (S)TEM imaging and electron diffraction analysis, this study also reveals the significant role of defects on the heterostructure growth. The direct growth technique applied here enables us to investigate the heterostructure nucleation and growth mechanisms at the atomic level without sample handling and transfer. Importantly, this approach can be utilized to study a wide spectrum of van der Waals heterostructures.
According to the standard protocol, a load-free healing period is one of the most emphasized requirements for implant integration. Recent studies have encouraged a progressive shortening of the healing period for single-tooth implants and immediate loading has been proposed for the aesthetic zone in the maxilla. The present study evaluated clinical outcomes of immediately loaded FRIALIT-2 Synchro implants 12 months after placement in the maxillary incisal region. In the course of our investigation, nine patients have been treated following an immediate loading protocol. The stepped-screw type implants were inserted with an increasing torque up to 45 Ncm, thus measuring the primary stability of the implants. All implants were immediately restored with unsplinted acrylic resin provisional crowns and the patients provided with occlusal splints. Regular controls were performed at monthly intervals, intraoral radiographs were taken directly after implant placement, 6 and 12 months post insertion. The survival rate, clinical stability (Periotest) and radiographic coronal bone defects (CBD) were evaluated at delivery of the definitive superstructures (CBD 6) and 6 months later (CBD 12). Twelve FRIALIT-2 Synchro stepped screws of 3.8, 4.5 and 5.5 mm diameter and 13 and 15 mm length were placed in the incisal maxillary region. The median Periotest value 6 months post insertion was -2 with a minimum of -5 and a maximum of +2. The mean coronal bone level changes (CBD) at 6 and 12 months were 0.45 and 0.75 mm. No implant failed up to 12 months after insertion, resulting in a 100% survival rate. The presented results showed promising data for immediately loaded single-tooth implants in the anterior maxilla. Periotest values were within the range published for submerged implants. The radiographic coronal bone resorption after 6 and 12 months was even less than evaluated for implants placed in a standard two-stage procedure. It is evident that successful immediate loading protocols require a careful and strict patient selection aimed at achieving the best primary stability and avoiding any excessive functional or non-functional loading. Additional research needs to be done to provide data in situations where problems of poor bone quality, multiple implants or augmentation procedures must be overcome.
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