Surface modification of polytetrafluoroethylene (PTFE) films is done by exposing the films to a sodium naphthalenide ( Na /naphtha) etchant, and esterification of 4,4'-azobis(4-cyanopentanoic acid) (ACP) with the hydroxyl groups covalently linked to the surface, followed by the surface-initiated free radical polymerization of 4-vinylpyridine (4 VP). The surface elemental composition and topography of the poly(4-vinylpyridine) (PVP) graft-functionalized PTFE surfaces (PTFE-g-PVP surfaces) were characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflectance (ATR) FTIR spectroscopy, and atomic force microscopy (AFM). Water contact angles on the pristine PTFE surface and PTFE-g-PVP surfaces were measured. The PVP brushes on the PTFE surface with well-preserved pyridine groups were used not only as the chemisorption sites for the palladium complexes (without the need for prior sensitization by SnCl 2) during the electroless plating of copper, but also as an adhesion promotion layer to enhance the adhesion of the electrolessly deposited copper to the PTFE surfaces. The T-peel adhesion strength of the electrolessly deposited copper to the PVP grafted PTFE (PTFE-g-PVP) surface could reach about 7.2 N/cm. This adhesion strength was much higher than that of the electrolessly deposited copper to the pristine or Na /naphtha-treated PTFE surface. Effects of the graft polymerization time and the activation time in the PdCl 2 solution on the T-peel adhesion strength of the electrolessly deposited copper (from the Sn -free process) to the PTFE-g-PVP surface were determined.
