Ultrafast Charge Transfer-Induced Unusual Nonlinear Optical Response in ReSe₂/ReS₂ Heterostructure

Ultrafast charge transfer in van der Waals heterostructures can effectively engineer the optical and electrical properties of two-dimensional semiconductors for designing photonic and optoelectronic devices. However, the nonlinear absorption conversion dynamics with the pump intensity and the underlying physical mechanisms in a type-II heterostructure remain largely unexplored, yet hold considerable potential for all-optical logic gates. Herein, two-dimensional ReSe 2 /ReS 2 heterostructure is designed to realize an unusual transition from reverse saturable absorption to saturable absorption (SA) with a conversion pump intensity threshold of approximately 170 GW/cm 2 . Such an intriguing phenomenon is attributed to the decrease of two-photon absorption (TPA) of ReS 2 and the increase of SA of ReSe 2 with the pump intensity. Based on the characterization results of X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, femtosecond transient absorption spectrum, Kelvin probe force microscopy, and density functional theory calculation, a type-II charge-transfer-energy level model is proposed combined with the TPA of ReS 2 and SA of ReSe 2 processes. The results reveal the critical role of ultrafast interfacial charge transfer in tuning the unusual nonlinear absorption and improving the SA of ReSe 2 /ReS 2 under different excitation wavelengths. Our finding deepens the understanding of nonlinear absorption physical mechanisms in two-dimensional heterostructure materials, which may further diversify the nonlinear optical materials and photonic devices.