Polymer metallization: Low energy ion beam surface modification to improve adhesion

The interface formation between copper and poly(ethylene terephthalate) (PET) and poly(methyl methacrylate) (PMMA) films is studied in situ by Ion Scattering Spectrometry (ISS). Very low metal fluxes(similar to 10(13) atoms/cm(2) s) and hence low deposition rates are obtained by using a Knudsen's effusion cell. This allows to reach very low metal coverages down to the sub-monolayer regime. The results indicate that without surface activation, Cu atoms interact only very weakly with both polymer surfaces. Indeed, the oxygen/carbon ISS intensify ratio remains nearly unaffected by the metal deposition, showing no preferential shadowing effect. Moreover, the ISS polymer signals are still detected after exposure to Cu atom fluences corresponding to several monolayers coverage. Cu diffusion below the polymer surface is evidenced by the presence of an inelastic multiple collision contribution in the ISS spectra. It is observed that 2 keV He-3(+) ion beam irradiation prior to metallization induces a drastic modification in the interface formation. Ion beam irradiation prevents the metal diffusion into the polymer bulk and leads to an increase of the metal concentration at the surface. In order to explain these results, the surface modifications produced by the ion beam on pristine polymers are studied by ISS and ToF-SIMS. Dehydrogenation and preferential loss of O containing fragments are found. These modifications are associated with the production of radicals leading to the creation of new adsorption sites for the Cu atoms. II is proposed that the reaction between radicals of different macrochains induces a surface crosslinking, that can prevent the diffusion for the deposited metal atoms into the polymer bulk.