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Ribbon Hero 2: Clippy's Second Chance, or just Ribbon Hero 2, is a video game developed by Microsoft Office Labs. The game is available as a free download and serves to educate users of Microsoft Word, Excel, PowerPoint and OneNote in Microsoft Office 2007 and 2010 how to use the ribbon interface. It is a sequel to Ribbon Hero.
Go Into the Story is the official blog for The Blacklist, the screenwriting community famous for its annual top ten list of unproduced scripts. One useful feature of Go Into the Story is its bank of downloadable movie scripts.
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Two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDs) have attracted tremendous interest for their broad-range applications in electronics, optoelectronics, catalysis, etc.1,2,3. The morphology or dimensionality of TMDs is a critical factor to determine their physical properties. For instance, one-dimension (1D) monolayer MoS2 ribbon is predicted to possess novel properties such as metallic edge states4, 1D confined plasmons5, ferromagnetic behaviors6, etc. Besides, it can present improved catalytic property in hydrogen evolution reaction (HER) due to the abundant active edge sites7, and more importantly, maintained high carrier mobility8. So far, the fabrication of monolayer TMDs ribbons has largely depended on micro-nanofabrication approaches, by using electron beam or optical lithography patterning techniques9. However, these top-down methods are evidently tedious and usually need to start with large-area uniform continuous films or crystals.
Recently, several strategies have been developed for the direct synthesis of monolayer TMDs ribbons10, such as Na-Mo-O droplets driven growth on NaCl single crystals11, substrate-directed synthesis on phosphine pre-treated Si(001) substrates12, as well as ledge-directed epitaxy on β-Ga2O3 (100)13. These strategies have individually achieved the control of their thickness, orientation and dimensionality, nevertheless, the synthesis of TMDs ribbons possessing all the above advantages has not been realized.
Herein, we design a substrate-step templated growth strategy for synthesizing large-area uniform, unidirectionally aligned, monolayer single-crystal TMDs ribbons, by using the step edges of vicinal Au(111) single crystals as growth fronts. The superiorities of this route are summarized as follows: (1) the uniformly oriented step edges on high-index Au facets can trigger the anisotropic growth of TMDs, and direct the alignment of the resulted monolayer ribbons; (2) the chemical inertness of Au substrate to chalcogen precursor makes it a universal template for synthesizing various monolayer TMDs ribbons (e.g., MoS2, WS2, MoSe2, WSe2); (3) different from the growth on insulating substrates, the monolayer TMDs grown on Au metals are featured with relatively strong interface coupling, which can be another parameter for mediating the van der Waals epitaxial growth of 2D layered materials toward wafer-scale single crystals; (4) the synergistic effect of substrate-step-edge guided 1D epitaxy, combined with substrate-lattice-match directed 2D epitaxy modes are expected to direct the epitaxial growth of single-crystal TMDs monolayers. This work is expected to offer an alternative strategy for the synthesis of monolayer patterned TMDs ribbons or wafer-scale single-crystal films. The practical applications of the dimension controllable monolayer materials (ribbons or films) will also be demonstrated in more versatile fields, e.g., as channel materials in high-performance electronic devices and as catalysts in HER.
To initialize the growth of monolayer MoS2 ribbons, it is a general route to introduce anisotropic template with broken symmetry, e.g., by introducing substrate steps27. Such a substrate-template-directed synthesis strategy has previously been used for the growth of 1D GaN28, graphene29, and MoS2 nanowires30. In our experiment, a series of high-miller-index Au facets vicinal to (111) with bunched atomic steps were selected as growth templates, as obtained by melting and resolidifying Au foils on W templates (see Methods for more details). As reported previously, the types of the MoS2 terminated edges were quite different for 1D stripes and 2D triangles, i.e., Mo-zigzag (Mo-zz)/S-zigzag (S-zz) edges and Mo-zz edges, respectively, as characterized by transmission electron microscope (TEM) in previous literatures27,28. Moreover, the edge type of monolayer MoS2 achieved by the CVD growth process highly depended on the S/Mo ratio of precursors31,32,33,34. In this regard, the effect of S/Mo ratio should have a significant effect on the morphology of monolayer MoS2.
According to our theoretical calculations, the following mechanism is proposed for the formation of unidirectionally oriented monolayer MoS2 ribbons. As schematically illustrated in Fig. 2a, MoS2 species tend to first nucleate at the step edges on the high-miller-index Au facets, considering of the high binding energy between them. Under a relatively small S/Mo ratio, the growth rate of S-zz edge was slower than that of Mo-zz edge, inducing the formation of MoS2 ribbons terminated by Mo-zz and S-zz edges on either side.
a Schematic illustration of the growth of well-aligned monolayer MoS2 ribbons along the step edges of vicinal Au(111) facets. The red, yellow, and blue spheres represent Mo, S, and O atoms, respectively, and the red arrows indicate the diffusion pathways of the active species. b, c Schematic side view and SEM image of aligned monolayer MoS2 ribbons grown on Au(223) facet, respectively. d Representative Raman spectra of the edges (red) and centers (blue) of monolayer MoS2 ribbons transferred on SiO2/Si substrates. e Raman mapping on the intensity of A1g peak for a MoS2 ribbon. The right panel is the magnified image of the white rectangle marked region in the left panel. The red and blue dots mark the edge and center positions of MoS2 ribbon, respectively. a.u., arbitrary units. f, g Representative PL spectra of the edges (red) and centers (blue) of a MoS2 ribbon and its PL mapping on the intensity of A peak. The right panel is the magnified image of the white rectangle marked region in the left panel. The red and blue dots in (g) mark the edge and center positions of MoS2 ribbon, respectively. h, i Schematic side view and SEM image of monolayer MoS2 ribbons grown on monolayer graphene covered Au(213) facet, respectively. j, k Schematic side view and SEM image of monolayer MoSxSe2-x ribbons grown along the steps of Au(235) facet, respectively.
The derived high-miller-index Au facets belong to a category of facets vicinal to Au(111), which are composed of a regular succession of (111) terraces separated by monatomic steps. Notably, the appearance of a specific high-index facet is relatively random, as similarly proposed in the preparation of atomic sawtooth high-miller-index Au facets through different annealing processes21. Herein, the formation of the high-index facet is probably due to the close contact between Au liquid and W template at high temperature, in which the strain energy should be the driving force, rather than the surface energy for the formation of Au(111). This phenomenon was also reported in the preparation of high-miller-index single-crystal Cu foils, in which the stress on Cu foil was introduced by using graphite susceptor41. Notably, a variety of vicinal Au(111) facets, independent of the specific index (e.g., Au(456), Au(346)), were all proved to be capable of inducing the formation of monolayer MoS2 ribbon arrays (Fig. 3e, f). Besides, the as-grown monolayer MoS2 ribbon presents a relatively high density on the high-miller-index Au facet with a high density of step (Supplementary Fig. 14). This provides an effective route for ribbon density regulation.
TEM and scanning transmission electron microscopy (STEM) characterizations were then conducted to identify the lattice orientation and edge structure. A representative atomically resolved STEM image presents well-ordered honeycomb lattices (Fig. 4h). On large scales, the crystal lattice of MoS2 maintains the same orientation, showing almost no obvious grain boundary. Selected-area electron diffraction (SAED) patterns collected on the film (Supplementary Fig. 16) reveal nearly identical lattice orientation (deviation smaller than ±0.1°), highly indicative of the single-crystal nature of the MoS2 film. Moreover, the edge types on both sides of the monolayer MoS2 ribbon are identified as Mo-zz and S-zz edges from both SAED pattern (Supplementary Fig. 17) and atomic-resolution STEM image (Fig. 4i), and this result is consistent with our previous calculations. Dark-field TEM images of the monolayer MoS2 film show uniform intensity over the entire area, again confirming its single crystallinity (Supplementary Fig. 18). 2b1af7f3a8