Ultraviolet saturable absorption and ultrafast carrier dynamics in ultrasmall black phosphorus quantum dots

Understanding the photoexcited carrier-relaxation actions in ultrasmall black phosphorus quantum dots (BPQDs) will play a crucial role in the fields of electronics and optoelectronics. Herein, we report the ultraviolet (UV) saturable absorption and ultrafast photoexcited carrier-relaxation dynamics of BPQDs. The ultrasmall BPQDs are synthesized using a facile liquid-exfoliation method and possess a diameter of 3.8 ± 0.6 nm and a thickness of 1.5 ± 0.4 nm. Femtosecond open-aperture (OA) Z-scan measurements showed typical saturable absorption properties in the UV band. A negative nonlinear optical (NLO) absorption coefficient of -(1.4 ± 0.3) × 10^-3 cm GW^-1 and a saturable intensity of 6.6 ± 1.3 GW cm^-2 were determined. Using a degenerate pump-probe technique, an ultrafast photoexcited carrier-recombination time was observed in the range of 216-305 fs, which was 3 orders of magnitude faster than that of BP nanosheets. Such an ultrafast relaxation component may be attributable to the edge- and step-mediated recombination and was confirmed by our density functional theory (DFT) calculations. This work provides fundamental insight into the underlying mechanism of the photoexcited carrier relaxation dynamic action in BPQDs which can enable UV photonic devices.