Sputtering of polymers by keV clusters: Microscopic views of the molecular dynamics

This article reviews the results of molecular dynamics simulations of cluster sputtering of hydrocarbon polymers obtained in the last few years and expand them with unpublished data of Ar cluster bombardment. The targets are molecular solids of linear hydrocarbons, polyethylene and polystyrene, including a polyethylene substrate decorated with adsorbed globular macromolecules. The projectiles are (hydro)carbon and Ar-n clusters, from small to massive, as well as Bi-n and Au-400 clusters. The study focuses on the dynamics of cratering and sputtering, using a coarse-grained representation of the samples, on the study of molecular fragmentation, crosslinking and free H formation, using a fully atomistic model, and on the conditions of desorption of macromolecules by massive clusters. The results explain the similarities and differences between several cluster types and sizes and, to a large extent, the sputtering yields of Ar-n clusters and their 'universal' dependence on the scaled cluster energy, as observed in the experiments. They also demonstrate the reduction of sample fragmentation and crosslinking when going to larger clusters and the incidence angle dependence of intact macromolecule emission. Recent experimental validations obtained in our laboratory are also introduced and comparisons with data obtained by other groups are discussed in order to present a more complete picture of the physics of cluster bombardment of organic solids and polymers. (C) 2014 Elsevier B.V. All rights reserved.