Molecular dynamics simulations of plasma-surface interactions

Molecular dynamics (MD) simulations are carried out to examine the fundamental mechanisms of plasma-surface interactions for various systems of interest to the semiconductor industry. These include ion and radical bombardment simulations of silicon, model low-k dielectric materials, and hydrocarbon (HC) based model photoresist materials.; Simulations of fluorocarbon (FC), fluorine, and argon ion etching of silicon are conducted to find conditions under which the steady state etch of Si in the presence of a FC surface layer occurs. By varying the FC/F/Ar + ratios over a range of conditions, a correlation between FC layer thickness and Si etch yield (EY) is obtained that agrees qualitatively with experimentally observed trends. Further examination of this system allows for a Si etch mechanism to be proposed. This mechanism is similar to that seen in previous Si etching simulations where FC films do not form. The FC layer is observed to fluctuate in thickness during steady state Si etch, as the result of competition between FC deposition and sputtering of relatively large (> 6 C atoms) FC clusters during Ar+ impacts. This cluster ejection process is seen in all of the systems studied, and the properties of these clusters (composition, size, kinetic energy, etc.) are examined and catalogued.; Ar+ and H radical and ion bombardment of a methylated Si surface is simulated as a model of plasma etching of low-k dielectric materials. The mechanisms and product distributions observed for 300 K H radical bombardment agree well with experiment. The etch characteristics of Ar+ bombardment are examined as a function of ion energy, and the corresponding variations in surface structure at high ion fluence are characterized.; Various HC polymer surfaces are studied under ion and radical bombardment to examine plasma species interactions with model photoresist materials. Simulations of 100 eV Ar+ bombardment of polystyrene (PS), poly(4-methylstyrene) (P4MS), and poly(alpha-methylstyrene) (PalphaMS) show that for all of these materials (which have similar chemical compositions: PS: (C8H 8)x, PalphaMS and P4MS: (C9H 10)x), a densely crosslinked, dehydrogenated damaged layer forms at high ion fluences that greatly reduces the sputter yield of the material. During the initial transient period of bombardment, PalphaMS shows sputter yields nearly twice as high as P4MS or PS; polymer structure can play a role during the early stages of etch. Both the initial and high fluence etch characteristics match those observed experimentally. Further, fluctuations from cell-to-cell are much higher for the PalphaMS simulations, which may correlate to the increased roughening observed experimentally for PalphaMS.; Additional simulations are carried out to examine the effects of H and F radical addition during Ar+ bombardment of PS. Both radical species are shown to inhibit and/or reverse the formation of the dehydrogenated layer that forms during bombardment with Ar+ alone. Further studies examine the effect of inert ion mass through simulations of Ar +, Xe+, and He+ bombardment of PS, amorphous C, and nanoscale features on diamond surfaces. The differences in penetration depth, kinetic energy deposition, and scattering patterns are suggestive of the differing etch characteristics that are seen experimentally for these ions. A discussion of dangling bond formation during ion bombardment and longer time-scale dynamics is also offered.; A brief review of currently available potential energy functions is presented. Selected results from MD simulations that utilize some of these potentials and are closely related to the work in this dissertation are also discussed. The difficulties of expanding potential energy functions vis-a-vis commonly used ab initio quantum chemical calculations are also addressed.