The utility of employing a variable duty cycle pulsed plasma polymerization technique to control film chemistry during plasma depositions is examined using allyl alcohol as monomer gas. Large scale progressive variations in film composition are observed with sequential changes in the plasma duty cycles employed, all other plasma variables being held constant. In particular, the −OH functionality of the monomer is increasingly retained in the plasma generated thin films as the radio frequency duty cycle is lowered. Fourier transform infrared and X-ray photoelectron spectroscopic analyses of the films obtained reveal that excellent film chemistry control is achieved during plasma polymerization of this monomer. The surface density controllability of functional groups, coupled with a gradient layering technique described herein to improve film adhesion to substrate surfaces, provides ideal opportunities for molecular tailoring of surfaces via subsequent derivatization reactions.

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EXPERIMENTAL MaterialsVinyl acetate, (VAc, Aldrich Chemicals, 99%) was stored over CaCl, and fractionally distilled. Vinylidene fluoride, (VF,, SCM Chemicals) was used after degassing.Trichlorotrifluoroethane (Isotron-113, surfactant) and t-butyl perpivalate (initiator, 75% in mineral spirits) were kindly supplied by the Pennwalt Corporation and used as received. Acetone-d, (99.9% with 0.05% TMS) was used for NMR analyses of the copolymers.