Preparation Of A Plasma Polymer Containing Phosphine Complexed Nickel By Concurrent Nickel Evaporation

This article describes one of the first examples of concurrent metal evaporation and substituted hydrocarbon plasma polymerization as a general method for preparing thin films containing a metal coordinated to a plasma polymer. In this report, the evaporation of Ni into a triallyl phosphine (TAP) glow discharge is described Deposition of a plasma polymer with concurrent reaction of Ni atoms with phosphine groups forms nickel containing triallyl phosphine plasma polymer, NiTAPPP. The chemical nature of the product is derived on the basis of infrared spectra taken of the film as formed and after reaction with air, CO, and NO. The extent of the reaction is deduced from gravimetric data obtained during reaction with CO and with NO; each case was followed by evacuation of the gas. The CO gravimetric data also suggest that uncoordinated Ni is predominantly formed at high (Ni evaporation rate)/(plasma polymer deposition rate) ratios; coordinated Ni predominates at low values of this parameter. The ESCA spectra are also obtained for this plasma polymer (NiTAPPP) as well as for that described in the previous paper, in which TAP is plasma polymerized (yielding TAPPP) and subsequently reacted with Ni(CO)4 (TAPPP + Ni(CO)4). In both cases, it was found that Ni is oxidized on contact with air. After such air exposure, ESCA spectra reveal the presence of residual Ni=P moieties on the surface of TAPPP + Ni(CO)4, but not of NiTAPPP. This is attributed to the greater reactivity of the coordinatively unsaturated Ni sites postulated for NiTAPPP. Copyright © 1992 John Wiley & Sons, Inc