Dissociative recombination as primary dissociation channel in plasma chemistry

Abstract

Molecule formation, surface modification and deposition in plasmas can in first order be described as dissociation in the plasma and association of fragments at the surface. In active plasmas ionization and dissociation by electrons is accompanied by excitation. But besides these direct electron processes also a second dissociation channel is active: that by charge transfer followed by dissociative recombination. This latter route is the dominant one in the colder recombining phase of the plasma. Atomic and molecular radicals diffuse or flow to the surface, where new molecules are formed. As a result the original molecules are, after being dissociated in the plasma, converted at the surface to new simple molecules, as H2, CO, N2, H2O, O2, NO, NH3, HCN, C2H2, CH4, to name a few in C/H/O/N containing plasmas. There is evidence that the molecular fragments resulting from dissociative recombination are ro-vibrationally (and possible electronically) excited. Also the molecules resulting from association at the surface may be ro-vibrationally or electronically excited. This may facilitate follow up processes as negative ion formation by dissociative attachment. These negative ions will be lost by mutual recombination with positive ions, giving again excited fragments. Rotational or other excitation may change considerably plasma chemistry.