Ang-Yu Lu

van der Waals Epitaxy of MoS2 Layers Using Graphene As Growth Templates

We present a method for synthesizing MoS(2)/Graphene hybrid heterostructures with a growth template of graphene-covered Cu foil. Compared to other recent reports, (1, 2) a much lower growth temperature of 400 °C is required for this procedure. The chemical vapor deposition of MoS(2) on the graphene surface gives rise to single crystalline hexagonal flakes with a typical lateral size ranging from several hundred nanometers to several micrometers. The precursor (ammonium thiomolybdate) together with solvent was transported to graphene surface by a carrier gas at room temperature, which was then followed by post annealing. At an elevated temperature, the precursor self-assembles to form MoS(2) flakes epitaxially on the graphene surface via thermal decomposition. With higher amount of precursor delivered onto the graphene surface, a continuous MoS(2) film on graphene can be obtained. This simple chemical vapor deposition method provides a unique approach for the synthesis of graphene heterostructures and surface functionalization of graphene. The synthesized two-dimensional MoS(2)/Graphene hybrids possess great potential toward the development of new optical and electronic devices as well as a wide variety of newly synthesizable compounds for catalysts.

High-Quality Thin Graphene Films from Fast Electrochemical Exfoliation

Flexible and ultratransparent conductors based on graphene sheets have been considered as one promising candidate for replacing currently used indium tin oxide films that are unlikely to satisfy future needs due to their increasing cost and losses in conductivity on bending. Here we demonstrate a simple and fast electrochemical method to exfoliate graphite into thin graphene sheets, mainly AB-stacked bilayered graphene with a large lateral size (several to several tens of micrometers). The electrical properties of these exfoliated sheets are readily superior to commonly used reduced graphene oxide, which preparation typically requires many steps including oxidation of graphite and high temperature reduction. These graphene sheets dissolve in dimethyl formamide (DMF), and they can self-aggregate at air-DMF interfaces after adding water as an antisolvent due to their strong surface hydrophobicity. Interestingly, the continuous films obtained exhibit ultratransparency (∼96% transmittance), and their sheet resistance is <1k Ω/sq after a simple HNO3 treatment, superior to those based on reduced graphene oxide or graphene sheets by other exfoliation methods. Raman and STM characterizations corroborate that the graphene sheets exfoliated by our electrochemical method preserve the intrinsic structure of graphene.

Direct Formation of Wafer Scale Graphene Thin Layers on Insulating Substrates by Chemical Vapor Deposition

Direct formation of high-quality and wafer scale graphene thin layers on insulating gate dielectrics such as SiO(2) is emergent for graphene electronics using Si-wafer compatible fabrication. Here, we report that in a chemical vapor deposition process the carbon species dissociated on Cu surfaces not only result in graphene layers on top of the catalytic Cu thin films but also diffuse through Cu grain boundaries to the interface between Cu and underlying dielectrics. Optimization of the process parameters leads to a continuous and large-area graphene thin layers directly formed on top of the dielectrics. The bottom-gated transistor characteristics for the graphene films have shown quite comparable carrier mobility compared to the top-layer graphene. The proposed method allows us to achieve wafer-sized graphene on versatile insulating substrates without the need of graphene transfer.

Janus monolayers of transition metal dichalcogenides

Structural symmetry-breaking plays a crucial role in determining the electronic band structures of two-dimensional materials. Tremendous efforts have been devoted to breaking the in-plane symmetry of graphene with electric fields on AB-stacked bilayers or stacked van der Waals heterostructures. In contrast, transition metal dichalcogenide monolayers are semiconductors with intrinsic in-plane asymmetry, leading to direct electronic bandgaps, distinctive optical properties and great potential in optoelectronics. Apart from their in-plane inversion asymmetry, an additional degree of freedom allowing spin manipulation can be induced by breaking the out-of-plane mirror symmetry with external electric fields or, as theoretically proposed, with an asymmetric out-of-plane structural configuration. Here, we report a synthetic strategy to grow Janus monolayers of transition metal dichalcogenides breaking the out-of-plane structural symmetry. In particular, based on a MoS2 monolayer, we fully replace the top-layer S with Se atoms. We confirm the Janus structure of MoSSe directly by means of scanning transmission electron microscopy and energy-dependent X-ray photoelectron spectroscopy, and prove the existence of vertical dipoles by second harmonic generation and piezoresponse force microscopy measurements.

Growth selectivity of hexagonal-boron nitride layers on Ni with various crystal orientations

Layered hexagonal-boron nitride (h-BN) films were synthesized by chemical vapor deposition (CVD) on Ni foils using ammonia borane as a precursor. Confocal Raman spectroscopy and electron backscatter diffraction (EBSD) were used to probe the effect of underlying Ni crystals with various orientations on growth behaviors of h-BN layers. The growth of the h-BN layers strongly depends on the Ni crystal orientations, where the growth rate of h-BN is larger on Ni(100)-like crystal surfaces but the growth on Ni(111)-like surfaces is not detectable, suggesting that Ni (100)-like facets are likely to promote the growth of h-BN compared with Ni (111)-like surfaces. The observation is in clear contrast to the reported growth of h-BN on Ni(111) in an ultrahigh vacuum environment. The as-grown CVD h-BN films on Ni exhibit a layered structure as revealed by atomic force microscopy (AFM). Thin h-BN layers are found on the Ni domain with a low growth rate. The observation of h-BN growth on various Ni grains may provide insights for the control of thickness, size and morphology of CVD h-BN films.

Photoluminescence Enhancement and Structure Repairing of Monolayer MoSe2 by Hydrohalic Acid Treatment

Atomically thin two-dimensional transition-metal dichalcogenides (TMDCs) have attracted much attention recently due to their unique electronic and optical properties for future optoelectronic devices. The chemical vapor deposition (CVD) method is able to generate TMDCs layers with a scalable size and a controllable thickness. However, the TMDC monolayers grown by CVD may incorporate structural defects, and it is fundamentally important to understand the relation between photoluminescence and structural defects. In this report, point defects (Se vacancies) and oxidized Se defects in CVD-grown MoSe2 monolayers are identified by transmission electron microscopy and X-ray photoelectron spectroscopy. These defects can significantly trap free charge carriers and localize excitons, leading to the smearing of free band-to-band exciton emission. Here, we report that the simple hydrohalic acid treatment (such as HBr) is able to efficiently suppress the trap-state emission and promote the neutral exciton and trion emission in defective MoSe2 monolayers through the p-doping process, where the overall photoluminescence intensity at room temperature can be enhanced by a factor of 30. We show that HBr treatment is able to activate distinctive trion and free exciton emissions even from highly defective MoSe2 layers. Our results suggest that the HBr treatment not only reduces the n-doping in MoSe2 but also reduces the structural defects. The results provide further insights of the control and tailoring the exciton emission from CVD-grown monolayer TMDCs.

Decoupling of CVD graphene by controlled oxidation of recrystallized Cu

Large-area graphene grown by chemical vapour deposition (CVD) is promising for applications; however, the interaction between graphene and the substrate is still not well understood. In this report, we use a combination of two non-destructive characterization techniques, i.e., electron backscatter diffraction (EBSD) and Raman mapping to locally probe the interface between graphene and copper lattices without removing graphene. We conclude that the crystal structure of the Cu grains under graphene layers is governed by two competing processes: (1) graphene induced Cu surface reconstruction favoring the formation of Cu(100) orientation, and (2) recrystallization from bulk Cu favoring Cu(111) formation. The underlying Cu grains, regardless of reconstruction or recrystallization, induce a large hydrostatic compression to the graphene lattice. Interestingly, the strong interaction could be decoupled by allowing the intercalation of a thin cuprous oxide interfacial-layer. The Cu2O layer is mechanically and chemically weak; hence, graphene films can be detached and transferred to arbitrary substrates and the Cu substrates could be re-used for graphene growth.

Three-Dimensional Heterostructures of MoS2 Nanosheets on Conducting MoO2 as an Efficient Electrocatalyst To Enhance Hydrogen Evolution Reaction

Molybdenum disulfide (MoS2) is a promising catalyst for hydrogen evolution reaction (HER) because of its unique nature to supply active sites in the reaction. However, the low density of active sites and their poor electrical conductivity have limited the performance of MoS2 in HER. In this work, we synthesized MoS2 nanosheets on three-dimensional (3D) conductive MoO2 via a two-step chemical vapor deposition (CVD) reaction. The 3D MoO2 structure can create structural disorders in MoS2 nanosheets (referred to as 3D MoS2/MoO2), which are responsible for providing the superior HER activity by exposing tremendous active sites of terminal disulfur of S2(-2) (in MoS2) as well as the backbone conductive oxide layer (of MoO2) to facilitate an interfacial charge transport for the proton reduction. In addition, the MoS2 nanosheets could protect the inner MoO2 core from the acidic electrolyte in the HER. The high activity of the as-synthesized 3D MoS2/MoO2 hybrid material in HER is attributed to the small onset overpotential of 142 mV, a largest cathodic current density of 85 mA cm(-2), a low Tafel slope of 35.6 mV dec(-1), and robust electrochemical durability.

One-Step Formation of a Single Atomic-Layer Transistor by the Selective Fluorination of a Graphene Film

In this study, the scalable and one-step fabrication of single atomic-layer transistors is demonstrated by the selective fluorination of graphene using a low-damage CF4 plasma treatment, where the generated F-radicals preferentially fluorinated the graphene at low temperature (<200 °C) while defect formation was suppressed by screening out the effect of ion damage. The chemical structure of the C-F bonds is well correlated with their optical and electrical properties in fluorinated graphene, as determined by X-ray photoelectron spectroscopy, Raman spectroscopy, and optical and electrical characterizations. The electrical conductivity of the resultant fluorinated graphene (F-graphene) was demonstrated to be in the range between 1.6 kΩ/sq and 1 MΩ/sq by adjusting the stoichiometric ratio of C/F in the range between 27.4 and 5.6, respectively. Moreover, a unique heterojunction structure of semi-metal/semiconductor/insulator can be directly formed in a single layer of graphene using a one-step fluorination process by introducing a Au thin-film as a buffer layer. With this heterojunction structure, it would be possible to fabricate transistors in a single graphene film via a one-step fluorination process, in which pristine graphene, partial F-graphene, and highly F-graphene serve as the source/drain contacts, the channel, and the channel isolation in a transistor, respectively. The demonstrated graphene transistor exhibits an on-off ratio above 10, which is 3-fold higher than that of devices made from pristine graphene. This efficient transistor fabrication method produces electrical heterojunctions of graphene over a large area and with selective patterning, providing the potential for the integration of electronics down to the single atomic-layer scale.

Transfer printing of graphene strip from the graphene grown on copper wires

A simple, cost-effective and lithography-free fabrication of graphene strips for device applications is demonstrated. The graphene thin layers were directly grown on Cu wires, followed by Cu etching and transfer printing to arbitrary substrates by a PDMS stamp. The Cu wires can be arranged on the PDMS stamp in a desired pattern; hence, the substrates can receive graphene strips with the same pattern. Moreover, the preparation of graphene strips does not involve conventional lithography; therefore, the surface of the graphene strip is free of residual photoresists, which may be useful for studies requiring clean graphene surfaces.