Atomically thin tungsten disulfide (WS2), a structural analogue to MoS2, has attracted great interest due to its indirect-to-direct band-gap tunability, giant spin splitting, and valley-related physics. However, the batch production of layered WS2 is underdeveloped (as compared with that of MoS2) for exploring these fundamental issues and developing its applications. Here, using a low-pressure chemical vapor deposition method, we demonstrate that high-crystalline mono- and few-layer WS2 flakes and even complete layers can be synthesized on sapphire with the domain size exceeding 50 × 50 μm(2). Intriguingly, we show that, with adding minor H2 carrier gas, the shape of monolayer WS2 flakes can be tailored from jagged to straight edge triangles and still single crystalline. Meanwhile, some intersecting triangle shape flakes are concomitantly evolved from more than one nucleus to show a polycrystalline nature. It is interesting to see that, only through a mild sample oxidation process, the grain boundaries are easily recognizable by scanning electron microscopy due to its altered contrasts. Hereby, controlling the initial nucleation state is crucial for synthesizing large-scale single-crystalline flakes. We believe that this work would benefit the controlled growth of high-quality transition metal dichalcogenide, as well as in their future applications in nanoelectronics, optoelectronics, and solar energy conversions.

Molybdenum disulfide (MoS2) is back in the spotlight because of the indirect-to-direct bandgap tunability and valley related physics emerging in the monolayer regime. However, rigorous control of the monolayer thickness is still a huge challenge for commonly utilized physical exfoliation and chemical synthesis methods. Herein, we have successfully grown predominantly monolayer MoS2 on an inert and nearly lattice-matching mica substrate by using a low-pressure chemical vapor deposition method. The growth is proposed to be mediated by an epitaxial mechanism, and the epitaxial monolayer MoS2 is intrinsically strained on mica due to a small adlayer-substrate lattice mismatch (~2.7%). Photoluminescence (PL) measurements indicate strong single-exciton emission in as-grown MoS2 and room-temperature PL helicity (circular polarization ~0.35) on transferred samples, providing straightforward proof of the high quality of the prepared monolayer crystals. The homogeneously strained high-quality monolayer MoS2 prepared in this study could competitively be exploited for a variety of future applications.

The atomic layer of hybridized hexagonal boron nitride (h-BN) and graphene has attracted a great deal of attention after the pioneering work of P. M. Ajayan et al. on Cu foils because of their unusual electronic properties (Ci, L. J.; et al. Nat. Mater. 2010, 9, 430-435). However, many fundamental issues are still not clear, including the in-plane atomic continuity as well as the edge type at the boundary of hybridized h-BN and graphene domains. To clarify these issues, we have successfully grown a perfect single-layer h-BN-graphene (BNC) patchwork on a selected Rh(111) substrate, via a two-step patching growth approach. With the ideal sample, we convinced that at the in-plane linking interface, graphene and h-BN can be linked perfectly at an atomic scale. More importantly, we found that zigzag linking edges were preferably formed, as demonstrated by atomic-scale scanning tunneling microscopy images, which was also theoretically verified using density functional theory calculations. We believe the experimental and theoretical works are of particular importance to obtain a fundamental understanding of the BNC hybrid and to establish a deliberate structural control targeting high-performance electronic and spintronic devices.

Wrinkles are ubiquitous for graphene films grown on various substrates by chemical vapor deposition at high temperature due to the strain induced by thermal mismatch between the graphene and substrates, which greatly degrades the extraordinary properties of graphene. Here we show that the wrinkle formation of graphene grown on Cu substrates is strongly dependent on the crystallographic orientations. Wrinkle-free single-crystal graphene was grown on a wafer-scale twin-boundary-free single-crystal Cu(111) thin film fabricated on sapphire substrate through strain engineering. The wrinkle-free feature of graphene originated from the relatively small thermal expansion of the Cu(111) thin film substrate and the relatively strong interfacial coupling between Cu(111) and graphene, based on the strain analyses as well as molecular dynamics simulations. Moreover, we demonstrated the transfer of an ultraflat graphene film onto target substrates from the reusable single-crystal Cu(111)/sapphire growth substrate. The wrinkle-free graphene shows enhanced electrical mobility compared to graphene with wrinkles.

In-plane heterostructure of hexagonal boron nitride and graphene (h-BN-G) has become a focus of graphene research owing to its tunable bandgap and intriguing properties. We report herein the synthesis of a quasi-freestanding h-BN-G monolayer heterostructure on a weakly coupled Ir(111) substrate, where graphene and h-BN possess distinctly different heights and surface corrugations. An atomically sharp zigzag type boundary has been found to dominate the patching interface between graphene and h-BN, as evidenced by high-resolution Scanning tunneling microscopy investigation as well as density functional theory calculation. Scanning tunneling spectroscopy studies indicate that the graphene and h-BN tend to exhibit their own intrinsic electronic features near the patching boundary. The present work offers a deep insight into the h-BN-graphene boundary structures both geometrically and electronically together with the effect of adlayer-substrate coupling.

Embedding non-hexagonal rings into sp2-hybridized carbon networks is considered a promising strategy to enrich the family of low-dimensional graphenic structures. However, non-hexagonal rings are energetically unstable compared to the hexagonal counterparts, making it challenging to embed non-hexagonal rings into carbon-based nanostructures in a controllable manner. Here, we report an on-surface synthesis of graphene-like nanoribbons with periodically embedded four- and eight-membered rings. The scanning tunnelling microscopy and atomic force microscopy study revealed that four- and eight-membered rings are formed between adjacent perylene backbones with a planar configuration. The non-hexagonal rings as a topological modification markedly change the electronic properties of the nanoribbons. The highest occupied and lowest unoccupied ribbon states are mainly distributed around the eight- and four-membered rings, respectively. The realization of graphene-like nanoribbons comprising non-hexagonal rings demonstrates a controllable route to fabricate non-hexagonal rings in nanoribbons and makes it possible to unveil their unique properties induced by non-hexagonal rings.

It is well established that strain and geometry could affect the band structure of graphene monolayer dramatically. Here we study the evolution of local electronic properties of a twisted graphene bilayer induced by a strain and a high curvature, which are found to strongly affect the local band structures of the twisted graphene bilayer. The energy difference of the two low-energy van Hove singularities decreases with increasing lattice deformation and the states condensed into well-defined pseudo-Landau levels, which mimic the quantization of massive chiral fermions in a magnetic field of about 100 T, along a graphene wrinkle. The joint effect of strain and out-of-plane distortion in the graphene wrinkle also results in a valley polarization with a significant gap. These results suggest that strained graphene bilayer could be an ideal platform to realize the high-temperature zero-field quantum valley Hall effect.

Grain boundaries (GBs) of hexagonal boron nitride (h-BN) grown on Cu(111) were investigated by scanning tunneling microscopy/spectroscopy (STM/STS). The first experimental evidence of the GBs composed of square-octagon pairs (4|8 GBs) was given, together with those containing pentagon-heptagon pairs (5|7 GBs). Two types of GBs were found to exhibit significantly different electronic properties, where the band gap of the 5|7 GB was dramatically decreased as compared with that of the 4|8 GB, consistent with our obtained result from density functional theory (DFT) calculations. Moreover, the present work may provide a possibility of tuning the inert electronic property of h-BN via grain boundary engineering.