Epitaxial single-crystal hexagonal boron nitride multilayers on Ni (111).

Large-area single-crystal monolayers of two-dimensional (2D) materials such as graphene1-3, hexagonal boron nitride (hBN)4-6 and transition metal dichalcogenides7,8 have been grown. hBN is considered to be the 'ideal' dielectric for 2D-materials-based field-effect transistors (FETs), offering the potential for extending Moore's law9,10. Although hBN thicker than a monolayer is more desirable as substrate for 2D semiconductors11,12, highly uniform and single-crystal multilayer hBN growth has yet to be demonstrated. Here we report the epitaxial growth of wafer-scale single-crystal trilayer hBN by a chemical vapour deposition (CVD) method. Uniformly aligned hBN islands are found to grow on single-crystal Ni (111) at early stage and finally to coalesce into a single-crystal film. Cross-sectional transmission electron microscopy (TEM) results show that a Ni23B6 interlayer is formed (during cooling) between the single-crystal hBN film and Ni substrate by boron dissolution in Ni. There are epitaxial relationships between hBN and Ni23B6 and between Ni23B6 and Ni. We also find that the hBN film acts as a protective layer that remains intact during catalytic evolution of hydrogen, suggesting continuous single-crystal hBN. This hBN transferred onto the SiO2 (300 nm)/Si wafer acts as a dielectric layer to reduce electron doping from the SiO2 substrate in MoS2 FETs. Our results demonstrate high-quality single-crystal  multilayered hBN over large areas, which should open up new pathways for making it a ubiquitous substrate for 2D semiconductors.

Second-Harmonic Young's Interference in Atom-Thin Heterocrystals.

Second-harmonic generation (SHG) is a nonlinear optical process that converts two identical photons into a new one with doubled frequency. Two-dimensional semiconductors represented by transition-metal dichalcogenides are highly efficient SHG media because of their excitonic resonances. Using spectral phase interferometry, here we directly show that SHG in heterobilayers of MoS2 and WS2 is governed by optical interference between two coherent SH fields that are phase-delayed differently in each material. We also quantified the frequency-dependent phase difference between the two, which agreed with polarization-resolved data and first-principles calculations on complex susceptibility. The second-harmonic analogue of Young's double-slit interference shown in this work demonstrates the potential of custom-designed parametric generation by atom-thick nonlinear optical materials.

Exciton-Sensitized Second-Harmonic Generation in 2D Heterostructures.

The efficient optical second-harmonic generation (SHG) of two-dimensional (2D) crystals, coupled with their atomic thickness, which circumvents the phase-match problem, has garnered considerable attention. While various 2D heterostructures have shown promising applications in photodetectors, switching electronics, and photovoltaics, the modulation of nonlinear optical properties in such heterosystems remains unexplored. In this study, we investigate exciton-sensitized SHG in heterobilayers of transition metal dichalcogenides (TMDs), where photoexcitation of one donor layer enhances the SHG response of the other as an acceptor. We utilize polarization-resolved interferometry to detect the SHG intensity and phase of each individual layer, revealing the energetic match between the excitonic resonances of donors and the SHG enhancement of acceptors for four TMD combinations. Our results also uncover the dynamic nature of interlayer coupling, as made evident by the dependence of sensitization on interlayer gap spacing and the average power of the fundamental beam. This work provides insights into how the interlayer coupling of two different layers can modify nonlinear optical phenomena in 2D heterostructures.

Critical Role of Surface Termination of Sapphire Substrates in Crystallographic Epitaxial Growth of MoS2 Using Inorganic Molecular Precursors.

A highly reproducible route for the epitaxial growth of single-crystalline monolayer MoS2 on a C-plane sapphire substrate was developed using vapor-pressure-controllable inorganic molecular precursors MoOCl4 and H2S. Microscopic, crystallographic, and spectroscopic analyses indicated that the epitaxial MoS2 film possessed outstanding electrical and optical properties, excellent homogeneity, and orientation selectivity. The systematic investigation of the effect of growth temperature on the crystallographic orientations of MoS2 revealed that the surface termination of the sapphire substrate with respect to the growth temperature determines the crystallographic orientation selectivity of MoS2. Our results suggest that controlling the surface to form a half-Al-terminated surface is a prerequisite for the epitaxial growth of MoS2 on a C-plane sapphire substrate. The insights on the growth mechanism, especially the significance of substrate surface termination, obtained through this study will aid in designing efficient epitaxial growth routes for developing single-crystalline monolayer transition metal dichalcogenides.