Two-dimensional superconducting MoSi2N4(MoN)4n homologous compounds.

The number and stacking order of layers are two important degrees of freedom that can modulate the properties of 2D van der Waals (vdW) materials. However, the layers' structures are essentially limited to the known layered 3D vdW materials. Recently, a new 2D vdW material, MoSi2N4, without known 3D counterparts, was synthesized by passivating the surface dangling bonds of non-layered 2D molybdenum nitride with elemental silicon, whose monolayer can be viewed as a monolayer MoN (-N-Mo-N-) sandwiched between two Si-N layers. This unique sandwich structure endows the MoSi2N4 monolayer with many fascinating properties and intriguing applications, and the surface-passivating growth method creates the possibility of tuning the layer's structure of 2D vdW materials. Here we synthesized a series of MoSi2N4(MoN)4n structures confined in the matrix of multilayer MoSi2N4. These super-thick monolayers are the homologous compounds of MoSi2N4, which can be viewed as multilayer MoN (Mo4n+1N4n+2) sandwiched between two Si-N layers. First-principles calculations show that MoSi2N4(MoN)4 monolayers have much higher Young's modulus than MoN, which is attributed to the strong Si-N bonds on the surface. Importantly, different from the semiconducting nature of the MoSi2N4 monolayer, the MoSi2N4(MoN)4 monolayer is identified as a superconductor with a transition temperature of 9.02 K. The discovery of MoSi2N4(MoN)4n structures not only expands the family of 2D materials but also brings a new degree of freedom to tailor the structure of 2D vdW materials, which may lead to unexpected novel properties and applications.

Intercalated architecture of MA2Z4 family layered van der Waals materials with emerging topological, magnetic and superconducting properties.

The search for new two-dimensional monolayers with diverse electronic properties has attracted growing interest in recent years. Here, we present an approach to construct MA2Z4 monolayers with a septuple-atomic-layer structure, that is, intercalating a MoS2-type monolayer MZ2 into an InSe-type monolayer A2Z2. We illustrate this unique strategy by means of first-principles calculations, which not only reproduce the structures of MoSi2N4 and MnBi2Te4 that were already experimentally synthesized, but also predict 72 compounds that are thermodynamically and dynamically stable. Such an intercalated architecture significantly reconstructs the band structures of the constituents MZ2 and A2Z2, leading to diverse electronic properties for MA2Z4, which can be classified according to the total number of valence electrons. The systems with 32 and 34 valence electrons are mostly semiconductors. Whereas, those with 33 valence electrons can be nonmagnetic metals or ferromagnetic semiconductors. In particular, we find that, among the predicted compounds, (Ca,Sr)Ga2Te4 are topologically nontrivial by both the standard density functional theory and hybrid functional calculations. While VSi2P4 is a ferromagnetic semiconductor and TaSi2N4 is a type-I Ising superconductor. Moreover, WSi2P4 is a direct gap semiconductor with peculiar spin-valley properties, which are robust against interlayer interactions. Our study thus provides an effective way of designing septuple-atomic-layer MA2Z4 with unusual electronic properties to draw immediate experimental interest.

Chemical vapor deposition of layered two-dimensional MoSi2N4 materials.

Identifying two-dimensional layered materials in the monolayer limit has led to discoveries of numerous new phenomena and unusual properties. We introduced elemental silicon during chemical vapor deposition growth of nonlayered molybdenum nitride to passivate its surface, which enabled the growth of centimeter-scale monolayer films of MoSi2N4 This monolayer was built up by septuple atomic layers of N-Si-N-Mo-N-Si-N, which can be viewed as a MoN2 layer sandwiched between two Si-N bilayers. This material exhibited semiconducting behavior (bandgap ~1.94 electron volts), high strength (~66 gigapascals), and excellent ambient stability. Density functional theory calculations predict a large family of such monolayer structured two-dimensional layered materials, including semiconductors, metals, and magnetic half-metals.

A Double Support Layer for Facile Clean Transfer of Two-Dimensional Materials for High-Performance Electronic and Optoelectronic Devices.

Clean transfer of two-dimensional (2D) materials grown by chemical vapor deposition is critical for their application in electronics and optoelectronics. Although rosin can be used as a support layer for the clean transfer of graphene grown on Cu, it has not been usable for the transfer of 2D materials grown on noble metals or for large-area transfer. Here, we report a poly(methyl methacrylate) (PMMA)/rosin double support layer that enables facile ultraclean transfer of large-area 2D materials grown on different metals. The bottom rosin layer ensures clean transfer, whereas the top PMMA layer not only screens the rosin from the transfer conditions but also improves the strength of the transfer layer to make the transfer easier and more robust. We demonstrate the transfer of monolayer WSe2 and WS2 single crystals grown on Au as well as large-area graphene films grown on Cu. As a result of the clean surface, the transferred WSe2 retains the intrinsic optical properties of the as-grown sample. Moreover, it does not require annealing to form good ohmic contacts with metal electrodes, enabling high-performance field effect transistors with mobility and ON/OFF ratio ∼10 times higher than those made by PMMA-transferred WSe2. The ultraclean graphene film is found to be a good anode for flexible organic photovoltaic cells with a high power conversion efficiency of ∼6.4% achieved.

High-Performance Sub-Micrometer Channel WSe2 Field-Effect Transistors Prepared Using a Flood-Dike Printing Method.

Printing technology has potential to offer a cost-effective and scalable way to fabricate electronic devices based on two-dimensional (2D) transition metal dichalcogenides (TMDCs). However, limited by the registration accuracy and resolution of printing, the previously reported printed TMDC field-effect transistors (FETs) have relatively long channel lengths (13-200 µm), thus suffering low current-driving capabilities (≤0.02 µA/µm). Here, we report a "flood-dike" self-aligned printing technique that allows the formation of source/drain metal contacts on TMDC materials with sub-micrometer channel lengths in a reliable way. This self-aligned printing technique involves three steps: (i) printing of gold ink on a WSe2 flake to form the first gold electrode, (ii) modifying the surface of the first gold electrode with a self-assembled monolayer (SAM) to lower the surface tension and render the surface hydrophobic, and (iii) printing of gold ink close to the SAM-treated first electrode at a certain distance. During the third step, the gold ink would first spread toward the edge of the first electrode and then get stopped by the hydrophobic SAM coating, ending up forming a sub-micrometer channel. With this printing technique, we have successfully downscaled the channel length to ∼750 nm and achieved enhanced on-state current densities of ∼0.64 µA/µm (average) and high on/off current ratios of ∼3 × 105 (average). Furthermore, with our high-performance printed WSe2 FETs, driving capabilities for quantum-dot light-emitting diodes (LEDs), inorganic LEDs, and organic LEDs have been demonstrated, which reveals the potential of using printed TMDC electronics for display backplane applications.

Ultrafast Growth of High-Quality Monolayer WSe2 on Au.

The ultrafast growth of high-quality uniform monolayer WSe2 is reported with a growth rate of ≈26 µm s-1 by chemical vapor deposition on reusable Au substrate, which is ≈2-3 orders of magnitude faster than those of most 2D transition metal dichalcogenides grown on nonmetal substrates. Such ultrafast growth allows for the fabrication of millimeter-size single-crystal WSe2 domains in ≈30 s and large-area continuous films in ≈60 s. Importantly, the ultrafast grown WSe2 shows excellent crystal quality and extraordinary electrical performance comparable to those of the mechanically exfoliated samples, with a high mobility up to ≈143 cm2 V-1 s-1 and ON/OFF ratio up to 9 × 106 at room temperature. Density functional theory calculations reveal that the ultrafast growth of WSe2 is due to the small energy barriers and exothermic characteristic for the diffusion and attachment of W and Se on the edges of WSe2 on Au substrate.