Silanization of Plasma-Activated Hexamethyldisiloxane-Based Plasma Polymers for Substrate-Independent Deposition of Coatings with Controlled Surface Chemistry

Plasma polymerization has emerged as an appealing technique for surface modification because of its advantages over a variety of conventional techniques, including ease-of-use and the possibility to modify nearly any substrate. One of the main challenges of plasma polymer-based surface modification, however, is having control over the coating chemistry, as plasma deposition generates a diversity of chemical structures. Therefore, this study presents an alternative plasma-based method for the fabrication of coatings that contain selective functionalities. In a first step, hexamethyldisiloxane (HMDSO) plasma polymerization is performed in a medium-pressure dielectric barrier discharge (DBD) to deposit polydimethylsiloxane (PDMS)-like coatings. In a second step, this coating is exposed to an air plasma in a similar DBD setup to introduce silanol groups on the surface. These groups are used in a third and final step as anchoring points for grafting of (3-aminopropyl)triethoxysilane (APTES) and (3-bromopropyl)trichlorosilane (BrPTCS) to selectively introduce amino or bromo groups, respectively. X-ray photoelectron spectroscopy (XPS) and water contact angle (WCA) measurements indicated that the first two steps were successful. Moreover, the coating could be synthesized on three different surfaces, namely, glass, ultrahigh-molecular-weight polyethylene, and polytetrafluoroethylene, indicating the wide applicability of the developed procedure. Afterward, XPS also proved that the APTES and BrPTCS grafting resulted in the formation of a coating containing primary amines and alkyl bromides, respectively, in combination with an organosilicon matrix containing silanol groups as remaining reactive groups, proving the successful synthesis of selective functional plasma-based coatings. The intermediate air-plasma-activation step was demonstrated to be necessary for successful and stable grafting of the final layer. In conclusion, this study established a general procedure for the development of coatings with selective functionality that can be applied on a wide variety of substrates for, e.g., biosensor applications, biomolecule, or polymer immobilization or for the synthesis of antibacterial coatings.