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Mirror twin grain boundary (MTB) defects, being a special type of high-symmetry one-dimensional (1D) defects in two-dimensional atomically thin transition metal dichalcogenides (TMDCs), have received considerable interest due to their unique structures and intriguing 1D properties. However, formation and distribution of MTBs in hybrid TMDC materials such as heterojunction remain scarcely studied. Herein, we investigate the spatial distribution, lattice registry and formation mechanism of MTBs in molecular beam epitaxy grown monolayer WSe2–MoSe2 lateral heterojunctions using atomic-resolution annular dark-field scanning transmission electron microscopy (ADF-STEM). MTBs manifest a much higher density in MoSe2 than in WSe2 domains with a few of them spanning coherently across the domain interface. Compositionally, a Mo-dominant rather than W-dominant configuration was observed in those MTBs located in WSe2 domains and its origin can be attributed to the preferable Mo substitution to W along the MTBs occurring at the later MoSe2 growth period. This proposed mechanism is supported by ab-initio density functional theory calculations and substitution dynamics captured by in-situ ADF-STEM. The present study deepens our understanding of MTBs in heterostructured TMDCs, which may also serve as an excellent platform for the exploration of intriguing 1D physics.

Defects play vital roles in tailoring structures and properties of materials including the atomically thin two-dimensional (2D) materials, and increasing demands are requested to find effective ways to realize the defect engineering, i.e., tuning the defects and thus the materials’ structure–property in a well-controlled way. Herein, we propose a novel method to tune the structures and configurations of one-dimensional (1D) line defects in monolayer MoS2 via mass transport induced structural transformation. By using atomic-resolved annular dark-field scanning transmission electron microscopy (ADF-STEM), we demonstrate in situ that sulfur vacancy line defect can be healed locally into defect-free MoS2 lattice via the desorption of Mo atoms from vacancy lines and adsorption into a moving Mo cluster. Furthermore, directional transport of Mo atoms (or Mo cluster) along the sulfur vacancy lines can induce the formation of Mo chains. Such a mass transport induced defect tuning provides more operational routes for the rational defect designing and property tuning in MoS2 as well as other related 2D materials.

An in-depth understanding and precise controlling of grain boundary (GB) motion at the atomic scale are crucial for grain growth and recrystallization in polycrystalline materials. So far, the reported studies mainly focus on the GB motion in the ideal bicrystal system, while the atomic mechanisms of GB motion in polycrystals remain poorly understood. Herein, taking two-dimensional (2D) hexagonal boron nitride (h-BN) as a model system, we experimentally investigated the atomic-scale mechanisms of the GB motion in 2D polycrystals. Since GB motion is directly related to the GB structures, this article is organized following the configurations of GBs, which can be divided into straight (including symmetric and asymmetric GBs) and curved GBs. We revealed that (I) for symmetric GBs, the shear-coupled motion alone is insufficient to drive the continuous GB motion in polycrystalline materials, and GB sliding is also needed. (II) For asymmetric GBs, GB motion follows a defaceting-faceting process, in which dislocation reactions are crucial. (III) For curved GBs, shear-coupled GB motion (during grain shrinking) leads to grain rotation, and the rotation direction highly depends on the misorientation angles. (IV) Finally, we will discuss the characteristics of binary lattice h-BN and find that partial dislocations participate in the GB motion at high misorientation angles (>38°). Our results build up the framework of the atomic-scale mechanisms of the GB motion in 2D polycrystalline materials and will be instructive for technological applications such as grain growth and GB engineering.

Assembling monolayers into a bilayer system unlocks the rotational free degree of van der Waals (vdW) homo/heterostructure, enabling the building of twisted bilayer graphene (tBLG) which possesses novel electronic, optical, and mechanical properties. Previous methods for preparation of homo/heterstructures inevitably leave the polymer residue or hexagonal boron nitride (h-BN) mask, which usually obstructs the measurement of intrinsic mechanical and surface properties of tBLG. Undoubtedly, to fabricate the designable tBLG with clean interface and surface is necessary but challenging. Here, we propose a simple and handy method to prepare atomically clean twisted bilayer graphene with controllable twist angles based on wetting-induced delamination. This method can transfer tBLG onto a patterned substrate, which offers an excellent platform for the observation of physical phenomena such as relaxation of moire pattern in marginally tBLG. These findings and insight should ultimately guide the designable packaging and atomic characterization of the two-dimensional (2D) materials.

Structural defects in crystals are generally believed to disrupt the symmetry of the pristine lattice, but sometimes, they can also serve as the constituent elements of new structures if they are arranged in a well-ordered pattern. Herein, choosing 2D transition metal dichalcogenides (TMDCs) as a model system, we successfully fabricated a novel group of 2D materials-M2X3 (M = Mo, W, X = S, Se) via the periodic assembly of chalcogen vacancy lines in their corresponding MX2 monolayers (such as MoS2). Our ab initio calculations further revealed that these monolayer M2X3 materials electronically exhibit quasi-direct narrow band-gap semiconducting characteristics, e.g., Eg = 0.89 eV for Mo2S3, and show ultra-high phonon-limited room-temperature carrier mobility up to ∼27 000 cm2 V−1 s−1 for electrons in Mo2S3. The emergence of these novel M2X3 materials expands the existing 2D family and provides new platforms for both fundamental research and practical applications, and the approach via the periodic assembly of ordered defects should also be applicable to other 2D materials.

Monolayer (ML) transition-metal dichalcogenides (TMDs) continue to attract research attention, and the heterojunctions formed by vertically stacking or laterally stitching two different TMDs, e.g.,...

Atomically thin transition-metal dichalcogenide (TMDC) heterostructures have attracted increasing attention because of their unprecedented potential in the fields of electronics and optoelectronics. However, selective growth of either lateral or vertical TMDC heterostructures remains challenging. Here, we report that lateral and vertical MoS2/MoSe2 epitaxial heterostructures can be successfully fabricated via a one-step growth strategy, which includes triggering by the concentration of sulfur precursor vapor and a high-temperature annealing process. Vertically stacked MoS2/MoSe2 heterostructures can be synthesized via control of the nucleation and growth kinetics, which is induced by high sulfur vapor concentration. The high-temperature annealing process results in the formation of fractured MoSe2 and in situ epitaxial growth of lateral MoSe2-MoS2 heterostructures. This study has revealed the importance of sulfur vapor concentration and high-temperature annealing processes in the controllable growth of MoSe2-MoS2 heterostructures, paving a new route for fabricating two-dimensional TMDC heterostructures.

Interlayer rotation and stacking were recently demonstrated as effective strategies for tuning physical properties of various two-dimensional materials. The latter strategy was mostly realized in hetero-structures with continuously varied stacking orders, which obscure the revelation of the intrinsic role of a certain stacking order in its physical properties. Here, we introduce inversion-domain-boundaries into molecular-beam-epitaxy grown MoSe2 homo-bilayers, which induce unusual-fractional lattice translations to their surrounding domains, accounting for the observed diversity of large-area and uniform stacking sequences. Unusual low-symmetric stacking orders were observed using transmission electron microscopy and detailed geometries were identified by density functional theory. A linear relation was also revealed between interlayer distance and stacking energy. These stacking sequences yield various energy alignments between the valence states at {\Gamma} and K, showing stacking dependent bandgaps and valence band tail states in the measured scanning tunneling spectroscopy. These results may benefit the design of two-dimensional multilayers with manipulable stacking orders., Comment: to be published in Nano Letters

Precise control and in-depth understanding of the interfaces is crucial for the functionality-oriented material design with desired properties. Herein, via modifying the long-standing bicrystal strategy, we proposed a novel nanowelding approach to build up interfaces between two-dimensional (2D) materials with atomic precision. This method enabled us, for the first time, to experimentally achieve the quasi-full-parameter-space grain boundaries (GBs) in 2D hexagonal boron nitride (h-BN). It further helps us unravel the long-term controversy and confusion on the registry of GBs in h-BN, including i) discriminate the relative contribution of the strain and chemical energy on the registry of GBs; ii) identify a new dislocation core- Frank partial dislocation and four new anti-phase boundaries; and iii) confirm the universal GB faceting. Our work provides a new paradigm to the exploiting of structural-property correlation of interfaces in 2D materials., 49 pages,26 figures

Monolayer (ML) transition-metal dichalcogenides (TMDs) continue to attract research attention, and the heterojunctions formed by vertically stacking or laterally stitching two different TMDs, e.g., MoSe

Atomically thin transition-metal dichalcogenide (TMDC) heterostructures have attracted increasing attention because of their unprecedented potential in the fields of electronics and optoelectronics. However, selective growth of either lateral or vertical TMDC heterostructures remains challenging. Here, we report that lateral and vertical MoS

The large bending stiffnesses of few-atoms-thick two-dimensional (2D) materials doesn't allow them to be bent into nanometer-sized tubes or cages. So, different than graphene, most 2D materials don't have corresponding one-dimensional (1D) nanotube or zero-dimensional (0D) cage structures. In this article, the authors proposed a new strategy to create nanometer-sized 1D or 0D structures of few-atoms-thick 2D materials by using a paper folding-like technique, namely origami approach, to create line defects on one side of the 2D material to induce sharp turns on its surface. Using molybdenum disulfide as an example, their theoretical analysis proved that the origami approach is powerful for creating different types of nanomaterials; some of them are experimentally observed before.

Large-area two-dimensional (2D) materials for technical applications can now be produced by chemical vapor deposition (CVD). Unfortunately, grain boundaries (GBs) are ubiquitously introduced as a result of the coalescence of grains with different crystallographic orientations. It is well known that the properties of materials largely depend on GB structures. Here, we carried out a systematic study on the GB structures in CVD-grown polycrystalline h-BN monolayer films by transmission electron microscope. Interestingly, most of these GBs are revealed to be formed via overlapping between neighboring grains, which are distinct from the covalently bonded GBs as commonly observed in other 2D materials. Further density functional theory (DFT) calculations show that the hydrogen plays an essential role in overlapping GB formation. This work provides an in-depth understanding of the microstructures and formation mechanisms of GBs in CVD-grown h-BN films, which should be informative in guiding the precisely controlled synthesis of large area single crystalline h-BN and other 2D materials., 12 pages, 14 figures

Suppressing the oppositely orientated hexagonal boron nitride (h-BN) domains during the growth is of great challenge due to its bipolar structure. It is found that h-BN domains grown on onefold symmetric Cu(102) or (103) share a unique orientation, with one zigzag edge of the h-BN triangles perpendicular to the symmetry axis of the substrate surface.

We propose a novel algorithm to numerically retrieve the phase of the exit-wave function from a high-resolution transmission electron microscopy (HRTEM) image of a weak-phase object material, e.g., graphene and hexagonal boron nitride monolayers. It theoretically only requires a single HRTEM image to retrieve the phase under the assumption of a weak-phase object. In addition, it can remove the effects of geometrical aberrations up to fifth order, and also improve the degraded information due to the finite temporal and spatial coherence. We further present its applications and successfully demonstrate the identification of the lattice atoms and line defects in single HRTEM image of graphene.

In this paper, we propose a multiple-ellipse fitting method to accurately determine the atomic column positions in transmission electron microscopy (TEM) images. The column is enclosed by a series of ellipses fitted from contour lines at equidistant intensity levels, and each atomic column is shaped by an averaged elliptical shape to obtain its positions. In particular, the intensity profile of the atomic column can be obtained by an elliptically rotational average based on its shape; therefore, the intensities of the neighbouring atomic column can be subtracted for each atomic column during subsequent position refinement. This method can achieve precision in the picometre range, and we quantitatively measure this precision by analysing an image containing two Gaussian-shaped atoms and some simulated high-resolution transmission electron microscopy (HRTEM) images of SrTiO3.

Two-dimensional hexagonal boron nitride (h-BN) single crystals with various shapes have been synthesized by chemical vapor deposition over the past several years. Here we report the formation of three-leaf dart (3LD)-shaped single crystals of h-BN on Cu foil by atmospheric-pressure chemical vapor deposition. The leaves of the 3LD-shaped h-BN are as long as 18 {\mu}m and their edges are smooth armchair on one side and stepped armchair on the other. Careful analysis revealed that surface oxygen plays an important role in the formation of the 3LD shape. Oxygen suppressed h-BN nucleation by passivating Cu surface active sites and lowered the edge attachment energy, which caused the growth kinetics to change to a diffusion-controlled mode., Comment: 7 pages,6 figures

A facile all-chemical vapor deposition approach is designed, which allows both sequentially grown Gr and monolayer MoS2 in the same growth process, thus allowing the direct construction of MoS2 /Gr vertical heterostructures on Au foils. A weak n-doping effect and an intrinsic bandgap of MoS2 are obtained from MoS2 /Gr/Au via scanning tunneling microscopy and spectroscopy characterization. The exciton binding energy is accurately deduced by combining photoluminescence measurements.

Graphene/hexagonal boron nitride (h-BN) heterostructures have attracted a great deal of attention in recent years due to their unique and complementary properties for use in a wide range of potential applications. However, it still remains a challenge to synthesize large-area high quality samples by a scalable growth method. In this work, we present the synthesis of both in-plane and stacked graphene/h-BN heterostructures on Cu foils by sequentially depositing h-BN via ion beam sputtering deposition (IBSD) and graphene with chemical vapor deposition (CVD). Due to a significant difference in the growth rate of graphene on h-BN and Cu, the in-plane graphene/h-BN heterostructures were rapidly formed on h-BN domain/Cu substrates. The large-area vertically stacked graphene/h-BN heterostructures were obtained by using the continuous h-BN film as a substrate. Furthermore, the well-designed sub-bilayered h-BN substrates provide direct evidence that the monolayered h-BN on Cu exhibits higher catalytic activity than the bilayered h-BN on Cu. The growth method applied here may have great potential in the scalable preparation of large-area high-quality graphene/h-BN heterostructures.

Transition metal dichalcogenides (TMDs) are a family of van der Waals layered materials exhibiting unique electronic, optical, magnetic and transport properties. Their technological potentials hinge critically on the ability to achieve controlled fabrication of desirable nanostructures, such as nanoribbons and nanodots. To date, nanodots/nanoislands have been regularly observed, while controlled fabrication of TMD nanoribbons remains challenging. Here we report a bottom-up fabrication of MoSe2 nanoribbons using molecular beam epitaxy, via an unexpected temperature-induced morphological phase transition from the nanodot to nanoribbon regime. Such nanoribbons are of zigzag nature, characterized by distinct chemical and electronic properties along the edges. The phase space for nanoribbon growth is narrowly defined by proper Se:Mo ratios, as corroborated experimentally using different Se fluxes, and supported theoretically using first-principles calculations that establish the crucial role of the morphological reconstruction of the bare Mo-terminated edge. The growth mechanism revealed should be applicable to other TMD systems. The unique electronic properties of two-dimensional materials are determined not only by their shape, but also the precise atomic arrangement of atoms along edges. Here, Chenet al. have developed a bottom-up epitaxial growth of MoSe2nanoribbons that controls both geometry and edge states.

Understanding the influence of grain boundaries (GBs) on the electrical and thermal transport properties of graphene films is essentially important for electronic, optoelectronic and thermoelectric applications. Here we report a segregation–adsorption chemical vapour deposition method to grow well-stitched high-quality monolayer graphene films with a tunable uniform grain size from ∼200 nm to ∼1 μm, by using a Pt substrate with medium carbon solubility, which enables the determination of the scaling laws of thermal and electrical conductivities as a function of grain size. We found that the thermal conductivity of graphene films dramatically decreases with decreasing grain size by a small thermal boundary conductance of ∼3.8 × 109 W m−2 K−1, while the electrical conductivity slowly decreases with an extraordinarily small GB transport gap of ∼0.01 eV and resistivity of ∼0.3 kΩ μm. Moreover, the changes in both the thermal and electrical conductivities with grain size change are greater than those of typical semiconducting thermoelectric materials., Understanding the effect of grain boundaries on the electrical and thermal transport properties of graphene is of both fundamental and technological importance. Here, the authors fabricate graphene films with controlled grain size, and determine the scaling laws of thermal and electrical conductivities.

Transition metal dichalcogenides (TMDs) are a family of van der Waals layered materials exhibiting unique electronic, optical, magnetic and transport properties. Their technological potentials hinge critically on the ability to achieve controlled fabrication of desirable nanostructures, such as nanoribbons and nanodots. To date, nanodots/nanoislands have been regularly observed, while controlled fabrication of TMD nanoribbons remains challenging. Here we report a bottom-up fabrication of MoSe2 nanoribbons using molecular beam epitaxy, via an unexpected temperature-induced morphological phase transition from the nanodot to nanoribbon regime. Such nanoribbons are of zigzag nature, characterized by distinct chemical and electronic properties along the edges. The phase space for nanoribbon growth is narrowly defined by proper Se:Mo ratios, as corroborated experimentally using different Se fluxes, and supported theoretically using first-principles calculations that establish the crucial role of the morphological reconstruction of the bare Mo-terminated edge. The growth mechanism revealed should be applicable to other TMD systems., The unique electronic properties of two-dimensional materials are determined not only by their shape, but also the precise atomic arrangement of atoms along edges. Here, Chen et al. have developed a bottom-up epitaxial growth of MoSe2 nanoribbons that controls both geometry and edge states.

A periodic modulation of the local bandgap in the rotationally aligned MoS2/WSe2 bilayer creates a 2D electronic superlattice., By using direct growth, we create a rotationally aligned MoS2/WSe2 hetero-bilayer as a designer van der Waals heterostructure. With rotational alignment, the lattice mismatch leads to a periodic variation of atomic registry between individual van der Waals layers, exhibiting a Moiré pattern with a well-defined periodicity. By combining scanning tunneling microscopy/spectroscopy, transmission electron microscopy, and first-principles calculations, we investigate interlayer coupling as a function of atomic registry. We quantitatively determine the influence of interlayer coupling on the electronic structure of the hetero-bilayer at different critical points. We show that the direct gap semiconductor concept is retained in the bilayer although the valence and conduction band edges are located at different layers. We further show that the local bandgap is periodically modulated in the X-Y direction with an amplitude of ~0.15 eV, leading to the formation of a two-dimensional electronic superlattice.

The growth of high-quality two-dimensional (2D) layered chalcogenide crystals is highly important for practical applications in future electronics, optoelectronics, and photonics. Current route for the synthesis of 2D chalcogenide crystals by vapor deposition method mainly involves an energy intensive high-temperature growth process on solid substrates, often suffering from inhomogeneous nucleation density and grain size distribution. Here, we first demonstrate a facile vapor-phase synthesis of large-area high-quality 2D layered chalcogenide crystals on liquid metal surface with relatively low surface energy at a growth temperature as low as ∼100 °C. Uniform and large-domain-sized 2D crystals of GaSe and GaxIn1-xSe were grown on liquid metal surface even supported on a polyimide film. As-grown 2D GaSe crystals have been fabricated to flexible photodetectors, showing high photoresponse and excellent flexibility. Our strategy of energy-sustainable low-temperature growth on liquid metal surface may open a route to the synthesis of high-quality 2D crystals of Ga-, In-, Bi-, Hg-, Pb-, or Sn-based chalcogenides and halides.

Kilometer-scale continuous graphene fibers (GFs) with outstanding mechanical properties and excellent electrical conductivity are produced by high-throughput wet-spinning of graphene oxide liquid crystals followed by graphitization through a full-scale synergetic defect-engineering strategy. GFs with superior performances promise wide applications in functional textiles, lightweight motors, microelectronic devices, and so on.

Many transition-metal dichalcogenides, such as MoSe2, are direct-gap semiconductors at monolayer thickness, which hold potentials in nano-electronics, optoelectronics, and some new concept spin- and valley-electronic applications. For device application, however, controllable doping of the materials is essential. Here we report hole doping of epitaxial MoSe2 by nitrogen (N) plasma treatment with the aim of understanding the defect structure and its electronic characteristics. Examinations by annular dark field scanning transmission electron microscopy clearly reveal substitutional doping of N by replacing Se atoms in MoSe2 monolayer upon N-plasma treatment, though creation of Se vacancies are also possible. Interestingly, we note an unexpectedly high concentration of 'dual defects', where both Se atoms in the top and bottom Se layers of MoSe2 at the same lattice site are substituted by N and/or become vacant, suggesting a catalytic effect of defect formation. X-ray photoelectron spectroscopy and electron energy loss spectroscopy confirm the presence of N–Mo bonds. Photoemission spectroscopy reveals an impurity band as well as the Fermi level shift, confirming the p-type doping effect in MoSe2 monolayer by N-plasma treatment. Consistent with the PES results, scanning tunneling spectroscopy measurement also reveal defect states peaked at 0.6–0.7 eV above the valance band maximum. The effectiveness of N-doping is discussed.