Highly tunable nonlinear response of Au@WS₂ hybrids with plasmon resonance and anti-Stokes effect

We synthesize Au@WS2 hybrid nanobelts and investigate their third-order nonlinear responses mediated by a strong anti-Stokes effect. By using the femtosecond Z-scan technique and tuning the excitation photon energy (Eexc), we find the sign reversals of both nonlinear absorption coefficient β and nonlinear refractive index γ to be around 1.60 eV, which is prominently higher than the bandgap (1.35 eV) of WS2 bulk owing to the strong anti-Stokes processes around the bandgap of the indirect semiconductors. The saturable absorption and self-defocusing of the WS2 nanobelts are significantly enhanced by the plasmon resonance of the Au nanoparticles when Eexc > 1.60 eV. But the excited state absorption assisted by the anti-Stokes processes and the self-focusing observed at Eexc < 1.60 eV are suppressed by the surface plasmon. Furthermore, by using population rate equations, we theoretically analyze the sign reversals of both β and γ and reveal the physical mechanism of the unique nonlinear responses of the hybrids with the plasmon resonance and anti-Stokes effect. These observations enrich the understanding of the nonlinear processes and interactions between the plasmon and exciton and are helpful for developing nonlinear optical nanodevices.