Surface modification of two types of fluorinated polyimide (FPI) films, either by plasma polymerization and deposition of 4‐vinylpyridine (4VP) or by UV‐induced graft copolymerization with 4VP under atmospheric conditions, was carried out for adhesion enhancement with the electrolessly deposited copper. X‐ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) results revealed that the pyridine groups in the plasma polymerized 4VP (pp‐4VP) layer could be preserved to a large extent under proper glow discharge conditions. The grafted 4VP layer with well‐preserved pyridine groups was used not only as the chemisorption sites for the palladium complexes (without the need for prior sensitization by SnCl2) during the electroless plating of copper, but also as an adhesion promotion layer for the electrolessly deposited copper. The T‐peel adhesion strength of the electrolessly deposited copper with both the 4VP plasma‐polymerized FPI (pp‐4VP‐FPI) film and the 4VP graft‐copolymerized FPI (4VP‐g‐FPI) film was much higher than that of the electrolessly deposited copper with the pristine or the Ar plasma‐treated FPI films. The high adhesion strength between the electrolessly deposited copper and the surface‐modified FPI film was attributed to the fact that the plasma‐polymerized and the UV graft‐copolymerized 4VP chains were covalently tethered on the FPI surfaces, as well as the fact that these grafted 4VP polymer chains were spatially and reactively distributed into the copper matrix.
