Harmonic generation by atomic and nanoparticle precursors in a ZnS laser ablation plasma

Harmonic generation of a driving laser propagating across a laser ablation plasma serves for the diagnosis of multicomponent plumes. Here we study the contribution of atomic and nanoparticle precursors to the generation of coherent ultraviolet and vacuum ultraviolet light as low-order harmonics of the fundamental emission (1064 nm) of a Q-switched Nd:YAG laser in a nanosecond infrared ZnS laser ablation plasma. Odd harmonics from the 3rd up to the 9th order (118.2 nm) have been observed with distinct temporal and spatial characteristics which were determined by varying the delay between the ablation and driving nanosecond pulses and by spatially scanning the plasma with the focused driving beam propagating parallel to the target. At short distances from the target surface (<= 1 mm), the harmonic intensity displays two temporal components peaked at around 250 ns and 10 mu s. While the early component dies off quickly with increasing harmonic order and vanishes for the 9th order, the late component is notably intense for the 7th harmonic and is still clearly visible for the 9th. Spectral analysis of spontaneous plume emissions help to assign the origin of the two components. While the early plasma component is mainly constituted by neutral Zn atoms, the late component is mostly due to nanoparticles, which upon interaction with the driving laser are subject to breakup and ionization. With the aid of calculations of the phase matching integrals within the perturbative model of optical harmonic generation, these results illustrate how atom and nanoparticle populations, with differing temporal and spatial distributions within the ablation plasma, contribute to the nonlinear medium. (C) 2016 Elsevier B.V. All rights reserved.