Modification of plasma polymer films by ion implantation

In this work, thin polymer films were prepared from acetylene and argon radiofrequency (13.56 MHz, 80 W) glow discharges. Post-deposition treatment was performed by plasma immersion ion implantation in nitrogen or helium glow discharges (13.56 MHz, 70 W). In these cases, samples were biased with 25 kV negative pulses. Exposure time to the bombardment plasma, t, ranged from 900 to 7200 s. Chemical composition of the film surfaces was investigated by X-ray Photoelectron Spectroscopy and the resistance to oxidation by the etching process, in reactive oxygen plasmas. Oxygen and nitrogen were detected in all the samples. While the concentration of the former continuously changed with t, that of N kept practically constant in small proportions. The film is predominantly formed by sp² states, but the proportion of sp³ hybridization slightly increased with t. The etching rate dropped under certain conditions of nitrogen bombardment whereas helium implantation has not significantly improved it. These results are ascribed to the crosslinking degree of the polymeric chains, ruled by the total amount of energy delivered to the film.