This paper shows how structure and formation of metal-polymer interfac
es depend strongly on the preparation process and the interfacial chem
istry. Emphasis is placed on results obtained from trans mission elect
ron microscopy (TEM), X-ray photo electron spectroscopy (XPS), radiotr
acer measurements and computer simulations on the early stages of inte
rface formation during noble-metal deposition onto fully cured polymer
s. Noble metal atoms deposited onto polymers diffuse on and inside the
polymer and tend to agglomerate to clusters. XPS results show that no
significant diffusion occurs from larger clusters and is therefore al
so not expected from a continuous metal film. Thus the extent of diffu
sion into the polymer appears to be determined only by the initial sta
ge of the deposition process and increases strongly at low deposition
rates and elevated temperatures, where a large fraction of isolated me
tal atoms is able to diffuse into the polymer before being trapped by
other atoms at or near the surface. Our results point to a strong inte
rplay between chemical interaction, diffusion and agglomeration.