Defect-suppressed Submillimeter-Scale WS2 Single Crystals with High Photoluminescence Quantum Yields by Alternate-Growth-etching CVD

Defects, such as uncontrollable vacancies, will intensively degrade the material properties and device performance of CVD-grown transition metal dichalcogenides (TMDs). Although vacancies can be repaired by some post-processing measures, these treatments are usually time-consuming, complicated and may introduce uncontrollable chemical contaminants into TMDs. How to efficiently suppress the uncontrollable defects during CVD growth and acquire intrinsic high-quality CVD-grown TMDs without any after-treatment remains a critical challenge, and has not yet been well resolved. Here, an alternate-growth-etching (AGE) CVD method was demonstrated to fabricate defect-suppressed submillimeter-scale monolayer WS2 single crystals. Compared with normal CVD, the grain size of the as-grown WS2 can be enlarged by 4-5 times (∼520 μm) and the growth rate of ∼14.4 μm min-1 is also at a high level compared to reported results. Moreover, AGE-CVD can efficiently suppress atomic vacancies in WS2. In every growth-etching cycle, the etching of WS2 occurs preferentially at the defective sites, which will be healed at the following growth stage. As a result, WS2 monolayers obtained by AGE-CVD possess higher crystal quality, carrier mobility (8.3 cm2 V-1 s-1) and PL quantum yield (QY, 52.6%) than those by normal CVD. In particular, such a PL QY is the highest value ever reported for in situ CVD-grown TMDs without any after-treatment, and is even comparable to the values of mechanically exfoliated samples. This AGE-CVD method is also appropriate for the synthesis of other high-quality TMD single crystals on a large-scale.