Functionalization of Polymer Surfaces Using Excimer VUV Systems and Silent Discharges. Application to Electroless Metallization

New approaches for electroless plating of nonconductive polymers or polymer-based materials are described. In this work, polyimide substrates were surface-functionalized (i) in nitrogenated (ammonia at reduced pressure) and oxygenated (air at atmospheric pressure) atmospheres under assistance of vacuum-ultraviolet (VUV) irradiation (use of a xenon silent discharge excimer source) or (ii) directly in air at atmospheric pressure using a dielectric-barrier discharge (DBD) device. After functionalization, the substrates were “activated” by dipping in a dilute acidic PdCl₂ solution or by spin-coating of a thin metal-organic film (from a solution of palladium acetate (PdAc) in chloroform). The catalytic activity of the so-deposited palladium species toward the electroless deposition of nickel was studied before and after a VUV post-irradiation (in air at atmospheric or reduced pressure) with a view to understanding better the role of the reducer (sodium hypophosphite) within the electroless bath.

This work confirms the specific interest of grafting nitrogenated functionalities onto polymer surfaces for attaching covalently the palladium-based catalyst (in particular in the case of the PdCl₂ route), forming thus strong Pd - N - C bonds at the metal/polymer interface. This results from the strong chemical affinity of palladium toward nitrogen. On the other hand, when oxygenated functionalities are surface-grafted, the conventional two-step procedure using SnCl₂ and PdCl₂ solutions can be proposed due to the strong chemical affinity of tin toward oxygen. The Ni deposits obtained under these different conditions pass the standard Scotch^®-tape test and, therefore, exhibit a good practical adhesion. For this same purpose, it is interesting to note that the DBD treatment operating in air at atmospheric pressure causes an increase of the surface roughness and, therefore, an improvement in adhesion of metallic films when their initiation is catalyzed through the PdAc route. In addition, this work demonstrates that extensive research still has to be performed to understand and improve the Ni/polymer adhesion when the PdAc route associated with a VUV irradiation is considered.