Photochemical processes in laser ablation of organic solids: Molecular dynamics study.

摘要

In this thesis, a comprehensive study of the effect of the photochemical processes on laser ablation mechanisms has been conducted using molecular dynamics simulations.; We developed a new concept for modeling photochemical processes in laser ablation of organic films using a mesoscopic coarse-grain breathing sphere model for molecular dynamics simulations. The main advantage of our model is the ability to study the dynamics of the system at the mesoscopic length scale, a regime that is not accessible either with atomistic or continuum computational methods. The photodecomposition of the excited molecules and the chemical reaction patterns in our simulations are based on the photochemistry of chlorobenzene due to ease of its fragmentation and available experimental data. Interpretation of the experimental data is the main objective of our theoretical efforts.; Molecular dynamics simulations are used to investigate the effect of photochemical processes on molecular ejection mechanisms in 248-nm laser irradiation of organic solids. Photochemical reactions are found to release additional energy into the irradiated sample and decrease the average cohesive energy, therefore decreasing the value of the ablation threshold. The yield of emitted fragments becomes significant only above the ablation threshold. Below the ablation threshold, only the most volatile photoproduct, HCl, is ejected in very small amounts, whereas the remainder of photoproducts are trapped inside the sample. The presence of photochemical decomposition processes and subsequent chemical reactions changes the temporal and spatial energy deposition profile from pure photothermal ablation. The chemical reactions create an additional local pressure build up and, as a result, generate a strong and broad acoustic pressure wave propagating toward the bottom of the computational cell. The strong pressure wave in conjunction with the temperature increase in the absorbing region causes the ejection of hot massive molecular clusters. These massive clusters later disintegrate in the plume into the smaller clusters and monomers due to ongoing chemical reactions. The ejection and disintegration of big clusters result in the higher material removal rates and higher plume density. The results from our molecular dynamics simulations are in good agreement with experiment and provide microscopic perspective of photochemical processes in laser ablation to experimental investigations.; The ablation of material that is onset by pure photochemical processes has been investigated by molecular dynamics simulations. The simulations reveal that ablation by purely photochemical processes is accompanied by the ejection of relatively cold massive molecular clusters from the surface of the sample. The top of the plume exhibits high temperatures whereas the residual part of the sample is cold. The removal of the damaged material through big molecular cluster ejection is consistent with experimental observations of low heat damage of material. (Abstract shortened by UMI.)