Water‐Assisted Growth of Twisted 3R‐Stacked MoSe2 Spirals and Its Dramatically Enhanced Second Harmonic Generations

Enhanced second‐harmonic generation (SHG) responses are reported in monolayer transition metal dichalcogenides (e.g., MX2, M: Mo, W; X: S, Se) due to the broken symmetries. The 3R‐like stacked MX2 spiral structures possessing the similar broken inversion symmetry should present dramatically enhanced SHG responses, thus providing great flexibility in designing miniaturized on‐chip nonlinear optical devices. To achieve this, the first direct synthesis of twisted 3R‐stacked chiral molybdenum diselenide (MoSe2) spiral structures with specific screw dislocations (SD) arms is reported, via designing a water‐assisted chemical vapor transport (CVT) approach. The study also clarifies the formation mechanism of the MoSe2 spiral structures, by precisely regulating the precursor supply accompanying with multiscale characterizations. Significantly, an up to three orders of magnitude enhancement of the SHG responses in twisted 3R stacked MoSe2 spirals is demonstrated, which is proposed to arise from the synergistic effects of broken inversion symmetry, strong light–matter interaction, and band nesting effects. Briefly, the work provides an efficient synthetic route for achieving the 3R‐stacked TMDCs spirals, which can serve as perfect platforms for promoting their applications in on‐chip nonlinear optical devices. In this work, the twisted 3R‐stacked MoSe2 spirals with specific SD arms are successfully synthesized on SiO2/Si substrates for the first time, via designing a water‐assisted APCVT approach. Significantly, the broad available band response and up to three orders of magnitude enhancement of the SHG effects are demonstrated in twisted 3R stacked MoSe2 spirals.