Mechanistic Understanding of Excitation-Correlated Nonlinear Optical Properties in MoS₂ Nanosheets and Nanodots: The Role of Exciton Resonance

Low-dimensional molybdenum disulfide (MoS 2 ) materials such as nanosheets and nanodots exhibit exotic optical, electronic, and catalytic properties, but so far the limited understanding of their nonlinear optical properties has restricted their potential use in nonlinear optoelectronics. In this work, we demonstrate that chemically prepared MoS 2 nanosheets and nanodots have distinctive nonlinear emission properties: the former shows efficient second harmonic generation (SHG) with maximum intensity at its C-exciton resonance energy while the latter exhibits strong excitation-correlated two-photon luminescence (TPL). We combine two-photon photoluminescence excitation (TPPLE) and the Z -scan spectroscopies to study the second order response of the MoS 2 nanodots and reveal, for the first time, that the most efficient and tunable TPL occurs through resonant two-photon absorption (TPA) induced transition from the 1S h to 1P e exciton state, followed by phonon-mediated exciton relaxation (1P e → 1S e ) and fast transition to surface states at different energies. With this novel nonlinear spectroscopy approach, we determine the energy splitting between the 1S e and 1P e excitonic states to be 0.3 eV, which is slightly larger than that for MoS 2 monolayers, probably due to the stronger quantum confinement effect in the nanodots. We also observe a clear TPA saturation behavior in the MoS 2 NDs, and this is attributed to the state-filling effect in the 6-fold degenerate 1P e state. Finally, we demonstrate that these new fundamental understandings of the nonlinear absorption and emission properties of the MoS 2 NDs are critical for optimizing the performance of MoS 2 TPL-based multicolor cellular imaging.