Monolayers of transition metal dichalcogenides (TMDCs) have attracted a great interest for post‐silicon electronics and photonics due to their high carrier mobility, tunable bandgap, and atom‐thick 2D structure. With the analogy to conventional silicon electronics, establishing a method to convert TMDC to p‐ and n‐type semiconductors is essential for various device applications, such as complementary metal‐oxide‐semiconductor (CMOS) circuits and photovoltaics. Here, a successful control of the electrical polarity of monolayer WSe2 is demonstrated by chemical doping. Two different molecules, 4‐nitrobenzenediazonium tetrafluoroborate and diethylenetriamine, are utilized to convert ambipolar WSe2 field‐effect transistors (FETs) to p‐ and n‐type, respectively. Moreover, the chemically doped WSe2 show increased effective carrier mobilities of 82 and 25 cm2 V−1s−1 for holes and electrons, respectively, which are much higher than those of the pristine WSe2. The doping effects are studied by photoluminescence, Raman, X‐ray photoelectron spectroscopy, and density functional theory. Chemically tuned WSe2 FETs are integrated into CMOS inverters, exhibiting extremely low power consumption (≈0.17 nW). Furthermore, a p‐n junction within single WSe2 grain is realized via spatially controlled chemical doping. The chemical doping method for controlling the transport properties of WSe2 will contribute to the development of TMDC‐based advanced electronics.

Artificial van der Waals heterostructures of 2D layered materials are attractive from the viewpoint of the possible discovery of new physics together with improved functionalities. Stacking various combinations of atomically thin semiconducting transition metal dichalcogenides, MX 2 (M = Mo, W; X = S, Se, Te) with a hexagonal crystal structure, typically leads to the formation of a staggered Type II band alignment in the heterostructure, where electrons and holes are confined in different layers. Here, the comprehensive studies are performed on heterostructures prepared from monolayers of WSe 2 and MoTe 2 using differential reflectance, photoluminescence (PL), and PL excitation spectroscopy. The MoTe 2 /WSe 2 heterostructure shows strong PL from the MoTe 2 layer at ≈1.1 eV, which is different from the quenched PL from the WSe 2 layer. Moreover, enhancement of PL intensity from the MoTe 2 layer is observed because of the near-unity highly efficient photocarrier transfer from WSe 2 to MoTe 2 . These experimental results suggest that the MoTe 2 /WSe 2 heterostructure has a Type I band alignment where electrons and holes are confined in the MoTe 2 layer. The findings extend the diversity and usefulness of ultrathin layered heterostructures based on transition metal dichalcogenides, leading to possibilities toward future optoelectronic applications.

Bilayer graphene (BLG) comprises a 2D nanospace sandwiched by two parallel graphene sheets that can be used to intercalate molecules or ions for attaining novel functionalities. However, intercalation is mostly demonstrated with small, exfoliated graphene flakes. This study demonstrates intercalation of molybdenum chloride (MoCl ) into a large-area, uniform BLG sheet, which is grown by chemical vapor deposition (CVD). This study reveals that the degree of MoCl intercalation strongly depends on the stacking order of the graphene; twist-stacked graphene shows a much higher degree of intercalation than AB-stacked. Density functional theory calculations suggest that weak interlayer coupling in the twist-stacked graphene contributes to the effective intercalation. By selectively synthesizing twist-rich BLG films through control of the CVD conditions, low sheet resistance (83 Ω ▫ ) is realized after MoCl intercalation, while maintaining high optical transmittance (≈95%). The low sheet resistance state is relatively stable in air for more than three months. Furthermore, the intercalated BLG film is applied to organic solar cells, realizing a high power conversion efficiency.

Aligned growth of transition metal dichalcogenides and related two-dimensional (2D) materials is essential for the synthesis of high-quality 2D films due to effective stitching of merging grains. Here, we demonstrate the controlled growth of highly aligned molybdenum disulfide (MoS) on c-plane sapphire with two distinct orientations, which are highly controlled by tuning sulfur concentration. We found that the size of the aligned MoS grains is smaller and their photoluminescence is weaker as compared with those of the randomly oriented grains, signifying enhanced MoS-substrate interaction in the aligned grains. This interaction induces strain in the aligned MoS, which can be recognized from their high susceptibility to air oxidation. The surface-mediated MoS growth on sapphire was further developed to the rational synthesis of an in-plane MoS-graphene heterostructure connected with the predefined orientation. The in-plane epitaxy was observed by low-energy electron microscopy. Transmission electron microscopy and scanning transmission electron microscopy suggest the alignment of a zigzag edge of MoS parallel to a zigzag edge of the neighboring graphene. Moreover, better electrical contact to MoS was obtained by the monolayer graphene compared with a conventional metal electrode. Our findings deepen the understanding of the chemical vapor deposition growth of 2D materials and also contribute to the tailored synthesis as well as applications of advanced 2D heterostructures.

Recently, research on transition metal dichalcogenides (TMDCs) has been accelerated by the development of large-scale synthesis based on chemical vapor deposition (CVD). However, in most cases, CVD-grown TMDC sheets are composed of randomly oriented grains, and thus contain many distorted grain boundaries (GBs) which deteriorate the physical properties of the TMDC. Here, we demonstrate the epitaxial growth of monolayer tungsten disulfide (WS 2 ) on sapphire by introducing a high concentration of hydrogen during the CVD process. As opposed to the randomly oriented grains obtained in conventional growth, the presence of H 2 resulted in the formation of triangular WS 2 grains with the welldefined orientation determined by the underlying sapphire substrate. Photoluminescence of the aligned WS 2 grains was significantly suppressed compared to that of the randomly oriented grains, indicating a hydrogen-induced strong coupling between WS 2 and the sapphire surface that has been confirmed by density functional theory calculations. Scanning transmission electron microscope observations revealed that the epitaxially grown WS 2 has less structural defects and impurities. Furthermore, sparsely distributed unique dislocations were observed between merging aligned grains, indicating an effective stitching of the merged grains. This contrasts with the GBs that are observed between randomly oriented grains, which include a series of 8-, 7-, and alternating 7/5membered rings along the GB. The GB structures were also found to have a strong impact on the chemical stability and carrier transport of merged WS 2 grains. Our work offers a novel method to grow high-quality TMDC sheets with much less structural defects, contributing to the future development of TMDC-based electronic and photonic applications.

The development of bulk synthetic processes to prepare functional nanomaterials is crucial to achieve progress in fundamental and applied science. Transition-metal chalcogenide (TMC) nanowires, which are one-dimensional (1D) structures having three-atom diameters and van der Waals surfaces, have been reported to possess a 1D metallic nature with great potential in electronics and energy devices. However, their mass production remains challenging. Here, a wafer-scale synthesis of highly crystalline transition-metal telluride nanowires is demonstrated by chemical vapor deposition. The present technique enables formation of either aligned, atomically thin two-dimensional (2D) sheets or random networks of three-dimensional (3D) bundles, both composed of individual nanowires. These nanowires exhibit an anisotropic 1D optical response and superior conducting properties. The findings not only shed light on the controlled and large-scale synthesis of conductive thin films but also provide a platform for the study on physics and device applications of nanowire-based 2D and 3D crystals.

The in-plane connection and layer-by-layer stacking of atomically thin layered materials are expected to allow the fabrication of two-dimensional (2D) heterostructures with exotic physical properties and future engineering applications. However, it is currently necessary to develop a continuous growth process that allows the assembly of a wide variety of atomic layers without interface degradation, contamination, and/or alloying. Herein, we report the continuous heteroepitaxial growth of 2D multiheterostructures and nanoribbons based on layered transition metal dichalcogenide (TMDC) monolayers, employing metal organic liquid precursors with high supply controllability. This versatile process can avoid air exposure during growth process and enables the formation of in-plane heterostructures with ultraclean atomically sharp and zigzagedge straight junctions without defects or alloy formation around the interface. For the samples grown directly on graphite, we have investigated the local electronic density of states of atomically sharp heterointerface by scanning tunneling microscopy and spectroscopy, together with first-principles calculations. These results demonstrate an approach to realizing diverse nanostructures such as atomic layer-based quantum wires and superlattices and suggest advanced applications in the fields of electronics and optoelectronics.

No abstract