Initiated chemical vapor deposition (iCVD) is proposed as a novel all-dry method to produce polymer thin films. Unlike plasma enhanced CVD or plasma polymerization, iCVD is able to produce well-defined, stoichiometric polymer compositions without undesirable branching or crosslinking. iCVD can essentially be seen as a free radical polymerization but without the use of any liquid phase. It involves the thermal decomposition of an initiator in the gas phase, the adsorption of the activated initiator and monomer from the vapor phase onto a surface, and the subsequent radical polymerization on the surface to create a polymer coating.

We will show FTIR, XPS and NMR data to illustrate the variety of iCVD polymers, both homopolymer and copolymer systems of acrylates and methacrylates, that can be produced, demonstrating the stoichiometry and retention of chemical specificity in these materials. We will also give GPC and VASE (variable angle spectroscopic ellipsometry) results to quantify the deposition rate and molecular weight of these films. A kinetic model based on the proposed iCVD reaction mechanism which has been fitted to experimental data will also be presented to provide evidence that iCVD polymerization on a surface is analogous to radical polymerization in the bulk phase.