Ultrathin two-dimensional (2D) semiconducting layered materials offer a great potential to extend the Moore's Law (1). One key challenge for 2D semiconductors is to avoid the formation of charge scattering and trap sites from adjacent dielectrics. The insulating van der Waals layer, hexagonal boron nitride (hBN), is an excellent interface dielectric to 2D semiconductors, efficiently reducing charge scatterings (2, 3). Recent studies have shown the growth of single-crystal hBN films on molten Au surfaces (4) or bulk Cu foils (5). However, using molten Au is not favored in industry due to high cost, cross-contamination, and potential issues of process control and scalability. Cu foils may be suitable for roll-to-roll processes, but unlikely to be compatible with advanced microelectronic fabrication on Si wafers. Thus, only a reliable approach to grow single-crystal hBN on wafers can help realize the broad adoption of 2D layered materials in industry. Previous efforts on growing hBN triangular monolayers on Cu (111) metals have failed to achieve mono-orientation, resulting in unwanted grain boundaries when they merge as films (6,7). Growing singlecrystal hBN on such a high-symmetry surface planes (5,8) is commonly believed to be impossible even in theory. In stark contrast, we have successfully realized the epitaxial growth of single-crystal hBN monolayers on a Cu ( 111) thin film across a 2-inch c-plane sapphire wafer. This surprising result is corroborated by our first-principles calculations, suggesting that the epitaxy to the underlying Cu lattice is enhanced by the lateral docking to Cu (111) steps, to ensure the mono-orientation of hBN monolayers. The obtained singlecrystal hBN, incorporated as an interface layer between MoS2 and HfO2 in a bottom-gate configuration, has enhanced the electrical performance of transistors based on monolayer MoS2. This reliable approach of producing wafer-scale single-crystal hBN truly paves the way for developing futuristic 2D electronics.First, a single-crystal Cu (111) thin film on a wafer is needed. Single-crystal Cu in thick foils can be achieved through recrystallization induced by implanted seeds (5,9). However, for the formation of Cu (111) thin film on a wafer, the crystallinity strongly relies on the underlying substrate lattices. Here we used a c-plane sapphire as the substrate, on which a 500-nm-thick polycrystalline Cu film was sputtered followed by extensive thermal annealing to achieve singlecrystal Cu (111) films (10). One challenge is that Cu (111) tends to form twin grains separated by twin grain boundaries, through kinetic growth processes. Fig. 1a illustrates the atomic arrangements for the typical twinned Cu (111) structure. We find that the post-annealing at a high temperature (1,040 -1,070 °C) in the presence of hydrogen is the key to removing the twin grains, consistent with recent reports (10,11). Figures 1b and 1c show the optical micrographs (OMs) and electron backscatter diffraction (EBSD) patterns for the Cu (111) thin films after annealing at 1,000 °...

Two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDs) have emerged as attractive platforms in next-generation nanoelectronics and optoelectronics for reducing device sizes down to a 10 nm scale. To achieve this, the controlled synthesis of wafer-scale single-crystal TMDs with high crystallinity has been a continuous pursuit. However, previous efforts to epitaxially grow TMD films on insulating substrates (e.g., mica and sapphire) failed to eliminate the evolution of antiparallel domains and twin boundaries, leading to the formation of polycrystalline films. Herein, we report the epitaxial growth of wafer-scale single-crystal MoS2 monolayers on vicinal Au(111) thin films, as obtained by melting and resolidifying commercial Au foils. The unidirectional alignment and seamless stitching of the MoS2 domains were comprehensively demonstrated using atomic- to centimeter-scale characterization techniques. By utilizing onsite scanning tunneling microscope characterizations combined with first-principles calculations, it was revealed that the nucleation of MoS2 monolayer is dominantly guided by the steps on Au(111), which leads to highly oriented growth of MoS2 along the ⟨110⟩ step edges. This work, thereby, makes a significant step toward the practical applications of MoS2 monolayers and the large-scale integration of 2D electronics.

Palladium diselenide (PdSe2) is an emerging 2D layered material with anisotropic optical/electrical properties, extra‐high carrier mobility, excellent air stability, etc. So far, ultrathin PdSe2 is mainly achieved via mechanical exfoliation from its bulk counterpart, and the direct synthesis is still challenging. Herein, the synthesis of ultrathin 2D PdSe2 on conductive Au foil substrates via a facile chemical vapor deposition route is reported. Intriguingly, an anisotropic growth behavior is detected from the evolution of ribboned flakes with large length/width ratios, which is well explained from the orthorhombic symmetry of PdSe2. A unique even‐layered growth mode from 2 to 20 layers is also confirmed by the perfect combination of onsite scanning tunneling microscopy characterizations, through deliberately scratching the flake edge to expose both even and odd layers. This even‐layered, ribboned 2D material is expected to serve as a perfect platform for exploring unique physical properties, and for developing high‐performance electronic and optoelectronic devices.

Uncovering the thickness‐dependent electronic property and environmental stability for 2D materials are crucial issues for promoting their applications in high‐performance electronic and optoelectronic devices. Herein, the extrahigh air stability and giant tunable electronic bandgap of chemical vapor deposition (CVD)–derived few‐layer PdSe2 on Au foils, by using scanning tunneling microscope/spectroscopy (STM/STS), are reported. The robust stability of 2D PdSe2 is uncovered by the observation of nearly defect/adsorption‐free atomic lattices on long‐time air‐exposed samples. A one‐to‐one correspondence between the electronic bandgap (from ≈1.15 to ≈0 eV) and thickness of PdSe2/Au (from bilayer to bulk) is established. It is also revealed that few‐layer semiconducting PdSe2 flakes present zero‐gap edges, induced by hybridization of Pd 4d and Se 4p orbitals. This work hereby provides straightforward evidence for the thickness‐tunable electronic property and air stability of 2D semiconductors, thus shedding light on their applications in next‐generation electronic devices.

Two-dimensional (2D) semiconductors, especially transition metal dichalcogenides (TMDs), have been envisioned as promising candidates in extending Moore’s law. To achieve this, the controllable growth of wafer-scale TMDs single crystals or periodic single-crystal patterns are fundamental issues. Herein, we present a universal route for synthesizing arrays of unidirectionally orientated monolayer TMDs ribbons (e.g., MoS2, WS2, MoSe2, WSe2, MoSxSe2-x), by using the step edges of high-miller-index Au facets as templates. Density functional theory calculations regarding the growth kinetics of specific edges have been performed to reveal the morphological transition from triangular domains to patterned ribbons. More intriguingly, we find that, the uniformly aligned TMDs ribbons can merge into single-crystal films through a one-dimensional edge epitaxial growth mode. This work hereby puts forward an alternative pathway for the direct synthesis of inch-scale uniform monolayer TMDs single-crystals or patterned ribbons, which should promote their applications as channel materials in high-performance electronics or other fields.