laser-induced; plasma emission; molecular spectra;INDUCED-BREAKDOWN-SPECTROSCOPY; LOCAL THERMAL-EQUILIBRIUM; GAS-PHASE REACTIONS; ELEMENTAL ANALYSIS; ISOTOPIC SPECTROMETRY; SELF-ABSORPTION; INDUCED FLUORESCENCE; TITANIUM MONOXIDE; ABLATION PLUMES; FEMTOSECOND

The aim of this paper is the description of the optical emission spectral features of the plasma produced by laser-matter interaction, from a fundamental point of view. The laser induced plasma emission spectra are discussed in connection with the basic mechanisms that take place in the plasma phase at different time delays from the laser pulse. The laser induced plasma being a dynamic system, the hierarchy of the elementary mechanisms changes continuously because the electron number density and the electron temperature decrease during the expansion. As a consequence of this, over the duration of the plasma's persistence the prevailing emitting species changes from ions to atoms and from atoms to molecules. Both atomic and molecular emission spectroscopy are discussed, to convey a complete description of the temporal evolution of laser induced plasma. Current literature, as well as the traditional plasma theories, are presented and discussed in order to give to the reader a general idea of the potentialities and drawbacks of emission spectroscopy in the study of laser induced plasma and its various applications.

Laser-induced breakdown spectroscopy; Deep Sea; Double pulse; Cavitation bubble; High pressure;BULK AQUEOUS-SOLUTIONS; ELEMENTAL ANALYSIS; SINGLE-PULSE; SHOCK-WAVES; LIQUIDS; LIBS; EXCITATION; INTENSITY; ABLATION; INSIGHTS

There is a growing interest in the development of sensors use in exploration of the deep ocean. Techniques for the chemical analysis of submerged solids are of special interest, as they show promise for subsea mining applications where a rapid sorting of materials found in the sea bottom would improve efficiency. Laser-Induced Breakdown Spectroscopy (LIBS) has demonstrated potential for this application thanks to its unique capability of providing the atomic composition of submerged solids. Here we present a study on the parameters that affect the spectral response of metallic targets in an oceanic pressure environment. Following laser excitation of the solid, the plasma persistence and the cavitation bubble size are considerably reduced as the hydrostatic pressure increases. These effects are of particular concern in dual pulse excitation as reported here, where a careful choice of the interpulse timing is required. Shadowgraphic images of the plasma demonstrate that cavitation bubbles are formed early after the plasma onset and that the effect of hydrostatic pressure is negligible during the early stage of plasma expansion. Contrarily to what is observed at atmospheric pressure, emission spectra observed at high pressures are characterized by self-absorbed atomic lines on continuum radiation resulting from strong radiative recombination in the electron-rich confined environment. This effect is much less evident with ionic lines due to the much higher energy of the levels involved and ionization energy of ions, as well as to the lower extent of absorption effects occurring in the inner part of the plasma, where ionized species are more abundant. As a result of the smaller shorter-lived cavitation bubble, the LIBS intensity enhancement resulting from dual pulse excitation is reduced when the applied pressure increases. (C) 2017 Elsevier B.V. All rights reserved.

laser ablation in liquid; silver NPs; laser induced plasma; shockwave; bubble dynamics; water jet; thin water layer; bubble near a free surface;FREE-SURFACE; CAVITATION BUBBLES; LIQUID-JET; WAVE; NANOPARTICLES; COLLAPSE; GENERATION; BREAKDOWN; EROSION; YIELD

In this paper, emission spectroscopy and fast imaging surveys during pulsed laser ablation in liquid (PLAL) for nanoparticles (NPs) production have been used, in order to provide further details about the process involved and the potentialities offered by a wire-shaped sample ablated in a flowing water jet. This kind of set-up has been explored because the laser ablation efficiency in water increases when a thin water layer and a wire-shaped target are used. In order to understand the physical processes causing the increasing ablation efficiency, both the laser-induced plasma and bubble dynamics generated in a flowing liquid jet have been analysed. The plasma parameters and the bubble behaviour in such a system have been compared with those observed in conventional PLAL experiments, where either a bulk or a wire-shaped target is immersed in bulk water. From the data presented here it is evidenced that the plasma and shockwave induced during the breakdown process can play a direct role in the ablation efficiency variation observed. With regard to the cavitation bubbles evolving near a free surface (the interface between water and air) it should be noted that these have to be treated with caution as a consequence of the strong influence played in these circumstances by the boundary of the water jet during its expansion dynamics. The effects due to the size of the liquid layer, the presence of the water/air interface, the liquid characteristics, the target shape, the plasma evolution and the bubble dynamics together with their outcomes on the NPs' production, are presented and discussed.