| Laser-induced Breakdown Spectroscopy (LIBS) is a relatively new analytical diagnostic technique which has gained serious attention in recent past due to its simplicity, robustness, and portability and multi-element analysis capabilities. LIBS has been used successfully for analysis of elements in different media including solids, liquids and gases. Since 1963, when the first breakdown study was reported, to 1983, when the first LIBS experiments were reported, the technique has come a long way, but the majority of fundamental understanding of the processes that occur has taken place in last few years, which has propelled LIBS in the direction of being a well established analytical technique. This study, which mostly focuses on LIBS involving aerosols, has been able to unravel some of the mysteries and provide knowledge that will be valuable to LIBS community as a whole.;LIBS processes can be broken down to three basic steps, namely, plasma formation, analyte introduction, and plasma-analyte interactions. In this study, these three steps have been investigated in laser-induced plasma, focusing mainly on the plasma-particle interactions. Understanding plasma-particle interactions and the fundamental processes involved is important in advancing laser-induced breakdown spectroscopy as a reliable and accurate analytical technique. Critical understanding of plasma-particle interactions includes study of the plasma evolution, analyte atomization, and the particle dissociation and diffusion. In this dissertation, temporal and spatial studies have been done to understand the fundamentals of the LIBS processes including the breakdown of gases by the laser pulse, plasma inception mechanisms, plasma evolution, analyte introduction and plasma-particle interactions and their influence on LIBS signal. Spectral measurements were performed in a laser-induced plasma and the results reveal localized perturbations in the plasma properties in the vicinity of the analyte species, for first 60 mus. The measurements provide direct evidence of matrix effects in the LIBS plasma at early times. Electron density measurements at very early times in the plasma reveal deviations from the Local Thermodynamic Equilibrium conditions (LTE). The data from various experiments suggests a complex interaction between the plasma and the aerosol particle, during which the finite time-scales of particle dissociation, and heat and mass transfer are fundamental processes. |
