Growth Mechanism of Alternating Defect Domains in Hexagonal WS₂ via Inhomogeneous W-Precursor Accumulation

While a hexagonal WS₂ monolayer, grown by chemical vapor deposition, exhibits distinctive patterns in photoluminescence mapping, segmented with alternating S-vacancy (SV) and W-vacancy (WV) domains in a single crystal, the formation mechanism for native alternating defect domains remains unresolved to date. Here, the formation mechanism of alternating defect domains in hexagonal WS₂ via the precursor accumulation model is experimentally elucidated. A triangular WS₂ seed is initially formed, followed by a hexagonal flake. Alternating W-rich (SV) and W-deficient (WV) domains are constructed in hexagonal WS₂ flake, which is confirmed by confocal photoluminescence mapping and secondary ion mass spectroscopy. This is explained by the accumulation or scarcity of W-precursors at the edge of the WS₂ flake. The W-precursors accumulate near the edges of the initial triangular WS₂ seed over time, while they are deficient near the corners of the triangular WS₂ , eventually forming WV domains in the truncated hexagonal domains. The heterogeneous accumulation becomes more prominent in the presence of H₂ gas through desorption of the W-precursors.