Interpulse-Interval-Controlled Nanoparticle Formation in Gas-Phase Burst-Mode Femtosecond Laser Ablation

The formation and size evolution of gas-phase nanoparticles (NPs) in laser ablation inductively coupled plasma mass spectrometry critically influence aerosol transport, plasma ionization efficiency, and ultimately analytical accuracy. Nevertheless, burst-mode laser ablation, as an efficient and versatile strategy for controlling gas-phase NP size, remains insufficiently explored. Here, we combine experimental investigations and theoretical analysis to elucidate the mechanisms of gas-phase nanoparticle formation and size control by tuning the interpulse interval in burst-mode femtosecond (fs) laser ablation. The mean nanoparticle size exhibits a non-monotonic dependence on interpulse spacing, decreasing with a narrowing size distribution as the interval increases from 0 to 300 ps, and then increasing with distribution broadening at longer delays up to 1000 ps, closely correlating with ablation-crater depth. A characteristic transition at ~300 ps is identified, where both nanoparticle size and crater depth reach a minimum, revealing a critical timescale in pulse-plume-surface interactions. Simulations show that the interpulse interval governs the redistribution of laser energy between the surface and plume, driving a transition from surface-dominated ablation to plume-dominated absorption and partial recovery of surface coupling. This delay-dependent framework provides a unified explanation for nanoparticle formation, where particle size is determined by the competition between plume-mediated fragmentation and surface-driven material supply, and offers a basis for tailoring NP size distributions via temporal pulse shaping.