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 MoS 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.

The monolayer transition metal dichalcogenides have recently attracted much attention owing to their potential in valleytronics, flexible and low-power electronics, and optoelectronic devices. Recent reports have demonstrated the growth of large-size two-dimensional MoS2 layers by the sulfurization of molybdenum oxides. However, the growth of a transition metal selenide monolayer has still been a challenge. Here we report that the introduction of hydrogen in the reaction chamber helps to activate the selenization of WO3, where large-size WSe2 monolayer flakes or thin films can be successfully grown. The top-gated field-effect transistors based on WSe2 monolayers using ionic gels as the dielectrics exhibit ambipolar characteristics, where the hole and electron mobility values are up to 90 and 7 cm(2)/Vs, respectively. These films can be transferred onto arbitrary substrates, which may inspire research efforts to explore their properties and applications. The resistor-loaded inverter based on a WSe2 film, with a gain of ∼13, further demonstrates its applicability for logic-circuit integrations.

Advanced beyond-silicon electronic technology requires discoveries of both new channel materials and ultralow-resistance contacts 1,2 . Atomically thin two-dimensional (2D) semiconductors have great potential for realizing high-performance electronic devices 1,3 . However, because of metal-induced gap states (MIGS) 4-7 , energy barriers at the metalsemiconductor interface, which fundamentally lead to high contact resistances and poor current-delivery capabilities, have restrained the advancement of 2D semiconductor transistors to date 2,8,9 . Here, we report a novel ohmic contact technology between semimetallic bismuth and semiconducting monolayer transition metal dichalcogenides (TMDs) where MIGS is sufficiently suppressed and degenerate states in the TMD are spontaneously formed in contact with bismuth. Through this approach, we achieve zero Schottky barrier height, a record-low contact resistance (R C ) of 123 Ω μm, and a recordhigh on-state current density (I ON ) of 1135 µA µm -1 on monolayer MoS 2 . We also demonstrate that excellent ohmic contacts can be formed on various monolayer semiconductors, including MoS 2 , WS 2 , and WSe 2 . Our reported R C values are a significant improvement for 2D semiconductors, and approaching the quantum limit. This technology unveils the full potential of high-performance monolayer transistors that are on par with the state-of-the-art 3D semiconductors, enabling further device down-scaling and extending Moore's Law.The electrical contact resistance at a metal-semiconductor (M-S) interface has been an increasingly critical, yet unsolved issue for the semiconductor industry, hindering the ultimate

Optical second harmonic generation (SHG) is known as a sensitive probe to the crystalline symmetry of few-layer transition metal dichalcogenides (TMDs). Layer-number dependent and polarization resolved SHG have been observed for the special case of Bernal stacked few-layer TMDs, but it remains largely unexplored for structures deviated from this ideal stacking order. Here we report on the SHG from homo- and heterostructural TMD bilayers formed by artificial stacking with an arbitrary stacking angle. The SHG from the twisted bilayers is a coherent superposition of the SH fields from the individual layers, with a phase difference depending on the stacking angle. Such an interference effect is insensitive to the constituent layered materials and thus applicable to hetero-stacked bilayers. A proof-of-concept demonstration of using the SHG to probe the domain boundary and crystal polarity of mirror twins formed in chemically grown TMDs is also presented. We show here that the SHG is an efficient, sensitive, and nondestructive characterization for the stacking orientation, crystal polarity, and domain boundary of van der Waals heterostructures made of noncentrosymmetric layered materials.