There have been continuous efforts to seek novel functional two-dimensional semiconductors with high performance for future applications in nanoelectronics and optoelectronics. In this work, we introduce a successful experimental approach to fabricate monolayer phosphorene by mechanical cleavage and a subsequent Ar⁺ plasma thinning process. The thickness of phosphorene is unambiguously determined by optical contrast spectra combined with atomic force microscopy (AFM). Raman spectroscopy is used to characterize the pristine and plasma-treated samples. The Raman frequency of the A_2g mode stiffens, and the intensity ratio of A_2g to A_1g modes shows a monotonic discrete increase with the decrease of phosphorene thickness down to a monolayer. All those phenomena can be used to identify the thickness of this novel two-dimensional semiconductor. This work on monolayer phosphorene fabrication and thickness determination will facilitate future research on phosphorene.

Epitaxial growth of atomically thin two-dimensional crystals such as transition metal dichalcogenides remains challenging, especially for producing large-size transition metal dichalcogenides bilayer crystals featuring high density of states, carrier mobility and stability at room temperature. Here we achieve in epitaxial growth of the second monolayer from the first monolayer by reverse-flow chemical vapor epitaxy and produce high-quality, large-size transition metal dichalcogenides bilayer crystals with high yield, control, and reliability. Customized temperature profiles and reverse gas flow help activate the first layer without introducing new nucleation centers leading to near-defect-free epitaxial growth of the second layer from the existing nucleation centers. A series of bilayer crystals including MoS₂ and WS₂, ternary Mo_1−xW_xS₂ and quaternary Mo_1−xW_xS_2(1−y)Se_2y are synthesized with variable structural configurations and tunable electronic and optical properties. The robust, potentially universal approach for the synthesis of large-size transition metal dichalcogenides bilayer single crystals is highly-promising for fundamental studies and technological applications.