Abstract
In this presentation, first principles calculations combined with advanced surface diagnostics are used to unravel the mechanisms of plasma oxygen interaction with organic films, of interest for advanced patterning in semiconductor device manufacturing. Results from a combination of X-ray photoelectron spectroscopy (XPS) diagnosed oxygen plasma-exposed polystyrene films and first principles modeling of organic films (polystyrene, polyethylene and derivatives) provide insights into how organic films are oxidized by oxygen atoms. XPS measurements show the rapid formation of C-O structures and their saturation after oxygen exposure on both pristine and argon bombarded polystyrene samples. Quantum mechanics calculations confirm that C-OH formation can be immediate without recourse to previously formed dangling bonds. Multiple oxygen impacts are required for scission of pristine ethylene carbon strands. Therefore, ethylene films can be converted to polyols that are stable, whereas more likely strands are broken before polyol formation through the formation of water and C=O. On the contrary, intermediate compounds with adjacent C=O bonds are not likely to form stable structures. The combination of XPS measurements and modeling imply that the oxidation of polystyrene and polyethylene is self-limiting on both hydrogen saturated and de-hydrogenated (after argon ion plasma bombardment) surfaces.
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