Transience of plasma surface modification as an adhesion promoter for polychlorotrifluorethylene

Poly(chlorotrifluoroethylene) (PCTFE) and other fluoropolymers are increasingly used as inner layer dielectrics. However, these polymers have low surface energies and correspondingly poor adhesive properties. Results are presented on the use of a low-pressure ammonia plasma to enhance the surface bondability of PCTFE. The plasma modified PCTFE film surfaces were characterized by x-ray photoelectron spectroscopy and contact angle measurements. Surface modified films exhibited improved adhesion to electroless copper deposits (180 deg. peel test) compared to coated PCTFE controls and that underwent no plasma exposure. Annealing studies were conducted between 30 and 100 deg. C to examine the stability of the plasma-modified surfaces. For samples annealed below Tg, contact angle measurements indicated that the plasma-introduced groups remained bound on the surface for four weeks. For specimens annealed above Tg, the surface functionalities were absorbed within the bulk and surface rearrangement occurred within 10 h of annealing time. As a result of rearrangement, the benefit of adhesion enhancement by plasma is lost and the adhesion to copper is reduced