Stacking-controllable interlayer coupling and symmetric configuration of multilayered MoS2

The stacking order in layered transition-metal dichalcogenides (TMDCs) induces variations in the electronic and interlayer couplings. Therefore, controlling the stacking orientations when synthesizing TMDCs is desirable but remains a significant challenge. Here, we developed and showed the growth kinetics of different shapes and stacking orders in as-grown multi-stacked MoS2 crystals and revealed the stacking-order-induced interlayer separations, spin–orbit couplings (SOCs), and symmetry variations. Raman spectra in AA(A…)-stacked crystals demonstrated blueshifted out-of-plane (A1g) and in-plane (E2g1) phonon frequencies, representing a greater reduction of the van der Waals gap compared to conventional AB(A…)-stacking. Our observations, together with first-principles calculations, revealed distinct excitonic phenomena due to various stacking orientations. As a result, the photoluminescence emission was improved in the AA(A…)-stacking configuration. Additionally, calculations showed that the valence-band maxima (VBM) at the K point of the AA(A…)-stacking configuration was separated into multiple sub-bands, indicating the presence of stronger SOC. We demonstrated that AA(A…)-stacking emitted an intense second-harmonic signal (SHG) as a fingerprint of the more augmented non-centrosymmetric stacking and enabled SOC-induced splitting at the VBM. We further highlighted the superiority of four-wave mixing-correlated SHG microscopy to quickly resolve the symmetries and multi-domain crystalline phases of differently shaped crystals. Our study based on crystals with different shapes and multiple stacking configurations provides a new avenue for development of future optoelectronic devices. A method for investigating the relative alignment of stacks of two-dimensional layers has been developed by researchers in Korea. Two-dimensional materials, those just a single atom thick, have a host of unusual electronic and optical properties. Placing two-dimensional materials on top of each other to create thicker films offers a way to engineer further novel materials, but the properties of these stacks depend crucially on the relative orientation of each layer. Jong-Hyun Ahn from Yonsei University and colleagues synthesized stacks of molybdenum disulfide monolayers with various angular alignments using a technique called atmospheric-pressure chemical vapor deposition. They then characterized the structures optically and measured a gradual spectroscopic evolution induced by the varying the arrangement. This insight will be useful for designing future optoelectronic devices based on molybdenum disulfide monolayers. NaCl-assisted APCVD technique to synthesize multi-stacked MoS2 crystals with different stacking orientations and shape has been developed. We found that the stacking orientation of multi-stacked MoS2 crystals shows the underlying variation in the crystalline phases, symmetry inversion, spin–orbit coupling and interlayer interactions through intensive optical study based on Raman spectroscopy, PL spectroscopy and nonlinear technique of FWM correlated SHG imaging technique. Our study based on the crystals with different shape and multiple stacking configurations provide a new avenue for the possibilities of future optoelectronic devices.