Covalent Immobilization of Ultrathin Polymer Films by Thermal Activation of Perfluorophenyl Azide

The attachment of thin films on solid materials is an effective way to tailor the chemical and physical properties of the surface layer. In this article, we report an alternative approach to the covalent immobilization of ultrathin polymer films. The immobilization chemistry is based on the C−H/N−H insertion reaction of perfluorophenyl nitrenes that were generated by the thermal activation of perfluorophenyl azides (PFPAs). In the process, a silicon wafer was treated with PFPA-silane 1 to give a monolayer of azido groups on the surface. A polymer was then spin coated on the functionalized wafer and the sample was heated. Thermolysis produced perfluorophenyl nitrenes which underwent insertion reactions with the neighboring polymer chains. Removal of the excess polymer by solvent extraction resulted in nanometer-thick polymer thin films covalently attached to the wafer surface. Using polystyrene and poly(2-ethyl-2-oxazoline) as examples, covalently immobilized thin films with thicknesses ranging from a few to over a hundred Å were obtained. The thickness of the film could be controlled by the type and the molecular weight of the polymer. Patterned polymer films were also fabricated using this method.