Among large numbers of transition metal dichalcogenides (TMDCs), monolayer rhenium disulfide (ReS2) is of particular interest due to its unique structural anisotropy, which opens up unprecedented opportunities in dichroic atomical electronics. Understanding the domain structure and controlling the anisotropic evolution of ReS2 during the growth is considered critical for increasing the domain size toward a large-scale growth of monolayer ReS2. Herein, by employing angle-resolved Raman spectroscopy, we reveal that the hexagonal ReS2 domain is constructed by six well-defined subdomains with each b-axis parallel to the diagonal of the hexagon. By further combining the first-principles calculations and the transmission electron microscopy (TEM) characterization, a dislocation-involved anisotropic evolution is proposed to explain the formation of the domain structures and understand the limitation of the domain size. Based on these findings, growth rates of different crystal planes are well controlled to enlarge the domain size, and moreover, single-crystal domains with a triangle shape are obtained. With the improved domain size, large-scale uniform, strictly monolayer ReS2 films are grown further. Scalable field-effect transistor (FET) arrays are constructed, which show good electrical performances comparable or even superior to that of the single domains reported at room temperature. This work not only sheds light on comprehending the novel growth mechanism of ReS2 but also offers a robust and controllable strategy for the synthesis of large-area and high-quality two-dimensional materials with low structural symmetry.

Two unequal K and K' valleys in transition metal dichalcogenides (TMDC) enable large and controllable polarization, which is the cornerstone of emerging valleytronic applications. Here, a phase engineering strategy aided by resonant plasmonic coupling is proposed to manipulate the valley degree of freedom. Compared with the pristine WSe2 monolayer, the hybrid H/T phase WSe2 exhibits an enhanced degrees of circular polarization (DCP) and valley polarization (DVP). As further aided by the designed Au plasmonic array, the T phase facilitates the excitons process and promotes the charge transfer in WSe2/Au interface under the plasmonic‐enhanced electromagnetic field. Consequently, both the DCP and DVP values are considerably enhanced to 38.5% (15.6%) and 15.1% (7.6%) at 13 K (room temperature), respectively. Through finite difference time domain simulations (FDTD), the near‐field excitation, exciton decay, and far‐field detection processes are systematically analyzed, and highly consistent polarizations are quantitatively achieved between the theoretical and the experimental results. Accordingly, the high polarizations are revealed to be contributed by the increased exciton generation and radiation efficiency, chiral electromagnetic field, and non‐equilibrium spin distribution in the hybrid phase. The research presented here illustrates a promising route to control the spin and valley degrees of freedom in TMDC materials.

Transition-metal dichalcogenides with intrinsic spin-valley degree of freedom have enabled great potentials for valleytronic and optoelectronic applications. However, the degree of valley polarization is usually low under nonresonant excitation at room temperature due to the phonon-assisted intervalley scattering. Here, achiral and chiral Au arrays are designed to enhance the optical response and valley polarization in monolayer and bilayer WS2. A considerable band edge emission with 7 times increment is realized under the resonant coupling with Au dimer-prism arrays. Valley polarization enhancement is quantitatively predicted by the inherent mechanisms from elevated electromagnetic field intensity and radiation efficiency and further realized in polarized photoluminescence. A tunable valley polarization up to 30.0% is achieved in bilayer WS2 under a nonresonant excitation at room temperature. All of these results provide a promising route toward the development of room-temperature valley-dependent optoelectronic devices.