Wafer-scale single-crystal hexagonal boron nitride monolayers on Cu (111).

Ultrathin two-dimensional (2D) semiconducting layered materials offer great potential for extending Moore's law of the number of transistors in an integrated circuit1. One key challenge with 2D semiconductors is to avoid the formation of charge scattering and trap sites from adjacent dielectrics. An insulating van der Waals layer of hexagonal boron nitride (hBN) provides an excellent interface dielectric, efficiently reducing charge scattering2,3. Recent studies have shown the growth of single-crystal hBN films on molten gold surfaces4 or bulk copper foils5. However, the use of molten gold is not favoured by industry, owing to its high cost, cross-contamination and potential issues of process control and scalability. Copper foils might be suitable for roll-to-roll processes, but are unlikely to be compatible with advanced microelectronic fabrication on wafers. Thus, a reliable way of growing single-crystal hBN films directly on wafers would contribute to the broad adoption of 2D layered materials in industry. Previous attempts to grow hBN monolayers on Cu (111) metals have failed to achieve mono-orientation, resulting in unwanted grain boundaries when the layers merge into films6,7. Growing single-crystal hBN on such high-symmetry surface planes as Cu (111)5,8 is widely believed to be impossible, even in theory. Nonetheless, here we report the successful epitaxial growth of single-crystal hBN monolayers on a Cu (111) thin film across a two-inch c-plane sapphire wafer. This surprising result is corroborated by our first-principles calculations, suggesting that the epitaxial growth is enhanced by lateral docking of hBN to Cu (111) steps, ensuring the mono-orientation of hBN monolayers. The obtained single-crystal hBN, incorporated as an interface layer between molybdenum disulfide and hafnium dioxide in a bottom-gate configuration, enhanced the electrical performance of transistors. This reliable approach to producing wafer-scale single-crystal hBN paves the way to future 2D electronics.

Remarkably Deep Moiré Potential for Intralayer Excitons in MoSe2/MoS2 Twisted Heterobilayers.

A moiré superlattice formed in twisted van der Waals bilayers has emerged as a new tuning knob for creating new electronic states in two-dimensional materials. Excitonic properties can also be altered drastically due to the presence of moiré potential. However, quantifying the moiré potential for excitons is nontrivial. By creating a large ensemble of MoSe2/MoS2 heterobilayers with a systematic variation of twist angles, we map out the minibands of interlayer and intralayer excitons as a function of twist angles, from which we determine the moiré potential for excitons. Surprisingly, the moiré potential depth for intralayer excitons is up to ∼130 meV, comparable to that for interlayer excitons. This result is markedly different from theoretical calculations based on density functional theory, which show an order of magnitude smaller moiré potential for intralayer excitons. The remarkably deep intralayer moiré potential is understood within the framework of structural reconstruction within the moiré unit cell.

Wafer-scale single-orientation 2D layers by atomic edge-guided epitaxial growth.

Two-dimensional (2D) layered materials hold tremendous promise for post-Si nanoelectronics due to their unique optical and electrical properties. Significant advances have been achieved in device fabrication and synthesis routes for 2D nanoelectronics over the past decade; however, one major bottleneck preventing their immediate applications has been the lack of a reproducible approach for growing wafer-scale single-crystal films despite tremendous progress in recent experimental demonstrations. In this tutorial review, we provide a systematic summary of the critical factors-including crystal/substrate symmetry and energy consideration-necessary for synthesizing single-orientation 2D layers. In particular, we focus on the discussions of the atomic edge-guided epitaxial growth, which assists in unidirectional nucleation for the wafer-scale growth of single-crystal 2D layers.

Ledge-directed epitaxy of continuously self-aligned single-crystalline nanoribbons of transition metal dichalcogenides.

Two-dimensional transition metal dichalcogenide nanoribbons are touted as the future extreme device downscaling for advanced logic and memory devices but remain a formidable synthetic challenge. Here, we demonstrate a ledge-directed epitaxy (LDE) of dense arrays of continuous, self-aligned, monolayer and single-crystalline MoS2 nanoribbons on ß-gallium (III) oxide (ß-Ga2O3) (100) substrates. LDE MoS2 nanoribbons have spatial uniformity over a long range and transport characteristics on par with those seen in exfoliated benchmarks. Prototype MoS2-nanoribbon-based field-effect transistors exhibit high on/off ratios of 108 and an averaged room temperature electron mobility of 65 cm2 V-1 s-1. The MoS2 nanoribbons can be readily transferred to arbitrary substrates while the underlying ß-Ga2O3 can be reused after mechanical exfoliation. We further demonstrate LDE as a versatile epitaxy platform for the growth of p-type WSe2 nanoribbons and lateral heterostructures made of p-WSe2 and n-MoS2 nanoribbons for futuristic electronics applications.

Layer-Dependent and In-Plane Anisotropic Properties of Low-Temperature Synthesized Few-Layer PdSe2 Single Crystals.

Palladium diselenide (PdSe2), a peculiar noble metal dichalcogenide, has emerged as a new two-dimensional material with high predicted carrier mobility and a widely tunable band gap for device applications. The inherent in-plane anisotropy endowed by the pentagonal structure further renders PdSe2 promising for novel electronic, photonic, and thermoelectric applications. However, the direct synthesis of few-layer PdSe2 is still challenging and rarely reported. Here, we demonstrate that few-layer, single-crystal PdSe2 flakes can be synthesized at a relatively low growth temperature (300 °C) on sapphire substrates using low-pressure chemical vapor deposition (CVD). The well-defined rectangular domain shape and precisely determined layer number of the CVD-grown PdSe2 enable us to investigate their layer-dependent and in-plane anisotropic properties. The experimentally determined layer-dependent band gap shrinkage combined with first-principle calculations suggest that the interlayer interaction is weaker in few-layer PdSe2 in comparison with that in bulk crystals. Field-effect transistors based on the CVD-grown PdSe2 also show performances comparable to those based on exfoliated samples. The low-temperature synthesis method reported here provides a feasible approach to fabricate high-quality few-layer PdSe2 for device applications.

Asymmetry-enriched electronic and optical properties of bilayer graphene.

The electronic and optical response of Bernal stacked bilayer graphene with geometry modulation and gate voltage are studied. The broken symmetry in sublattices, one dimensional periodicity perpendicular to the domain wall and out-of-plane axis introduces substantial changes of wavefunctions, such as gapless topological protected states, standing waves with bonding and anti-bonding characteristics, rich structures in density of states and optical spectra. The wavefunctions present well-behaved standing waves in pure system and complicated node structures in geometry-modulated system. The optical absorption spectra show forbidden optical excitation channels, prominent asymmetric absorption peaks, and dramatic variations in absorption structures. These results provide that the geometry-modulated structure with tunable gate voltage could be used for electronic and optical manipulation in future graphene-based devices.

Bouncing jet: a Newtonian liquid rebounding off a free surface.

We find that a liquid jet can bounce off a bath of the same liquid if the bath is moving horizontally with respect to the jet. Previous observations of jets rebounding off a bath (e.g., the Kaye effect) have been reported only for non-Newtonian fluids, while we observe bouncing jets in a variety of Newtonian fluids, including mineral oil poured by hand. A thin layer of air separates the bouncing jet from the bath, and the relative motion replenishes the film of air. Jets with one or two bounces are stable for a range of viscosity, jet flow rate and velocity, and bath velocity. The bouncing phenomenon exhibits hysteresis and multiple steady states.

Tailoring Semiconductor Lateral Multijunctions for Giant Photoconductivity Enhancement.

Semiconductor heterostructures have played a critical role as the enabler for new science and technology. The emergence of transition-metal dichalcogenides (TMDs) as atomically thin semiconductors has opened new frontiers in semiconductor heterostructures either by stacking different TMDs to form vertical heterojunctions or by stitching them laterally to form lateral heterojunctions via direct growth. In conventional semiconductor heterostructures, the design of multijunctions is critical to achieve carrier confinement. Analogously, successful synthesis of a monolayer WS2 /WS2(1-x) Se2x /WS2 multijunction lateral heterostructure via direct growth by chemical vapor deposition is reported. The grown structures are characterized by Raman, photoluminescence, and annular dark-field scanning transmission electron microscopy to determine their lateral compositional profile. More importantly, using microwave impedance microscopy, it is demonstrated that the local photoconductivity in the alloy region can be tailored and enhanced by two orders of magnitude over pure WS2 . Finite element analysis confirms that this effect is due to the carrier diffusion and confinement into the alloy region. This work exemplifies the technological potential of atomically thin lateral heterostructures in optoelectronic applications.

Interlayer couplings, Moiré patterns, and 2D electronic superlattices in MoS2/WSe2 hetero-bilayers.

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.

Janus monolayers of transition metal dichalcogenides.

Structural symmetry-breaking plays a crucial role in determining the electronic band structures of two-dimensional materials. Tremendous efforts have been devoted to breaking the in-plane symmetry of graphene with electric fields on AB-stacked bilayers or stacked van der Waals heterostructures. In contrast, transition metal dichalcogenide monolayers are semiconductors with intrinsic in-plane asymmetry, leading to direct electronic bandgaps, distinctive optical properties and great potential in optoelectronics. Apart from their in-plane inversion asymmetry, an additional degree of freedom allowing spin manipulation can be induced by breaking the out-of-plane mirror symmetry with external electric fields or, as theoretically proposed, with an asymmetric out-of-plane structural configuration. Here, we report a synthetic strategy to grow Janus monolayers of transition metal dichalcogenides breaking the out-of-plane structural symmetry. In particular, based on a MoS2 monolayer, we fully replace the top-layer S with Se atoms. We confirm the Janus structure of MoSSe directly by means of scanning transmission electron microscopy and energy-dependent X-ray photoelectron spectroscopy, and prove the existence of vertical dipoles by second harmonic generation and piezoresponse force microscopy measurements.

Determination of band alignment in the single-layer MoS2/WSe2 heterojunction.

The emergence of two-dimensional electronic materials has stimulated proposals of novel electronic and photonic devices based on the heterostructures of transition metal dichalcogenides. Here we report the determination of band offsets in the heterostructures of transition metal dichalcogenides by using microbeam X-ray photoelectron spectroscopy and scanning tunnelling microscopy/spectroscopy. We determine a type-II alignment between MoS2 and WSe2 with a valence band offset value of 0.83 eV and a conduction band offset of 0.76 eV. First-principles calculations show that in this heterostructure with dissimilar chalcogen atoms, the electronic structures of WSe2 and MoS2 are well retained in their respective layers due to a weak interlayer coupling. Moreover, a valence band offset of 0.94 eV is obtained from density functional theory, consistent with the experimental determination.

Ultrahigh-gain photodetectors based on atomically thin graphene-MoS2 heterostructures.

Due to its high carrier mobility, broadband absorption, and fast response time, the semi-metallic graphene is attractive for optoelectronics. Another two-dimensional semiconducting material molybdenum disulfide (MoS2) is also known as light- sensitive. Here we show that a large-area and continuous MoS2 monolayer is achievable using a CVD method and graphene is transferable onto MoS2. We demonstrate that a photodetector based on the graphene/MoS2 heterostructure is able to provide a high photogain greater than 10(8). Our experiments show that the electron-hole pairs are produced in the MoS2 layer after light absorption and subsequently separated across the layers. Contradictory to the expectation based on the conventional built-in electric field model for metal-semiconductor contacts, photoelectrons are injected into the graphene layer rather than trapped in MoS2 due to the presence of a perpendicular effective electric field caused by the combination of the built-in electric field, the applied electrostatic field, and charged impurities or adsorbates, resulting in a tuneable photoresponsivity.