Laser Direct Writing of Arbitrary Complex Polymer Microstructures by Nitroxide-Mediated Photopolymerization

In this paper, we demonstrate the possibility of generating arbitrary polymer microstructures covalently linked to a first polymer layer by laser direct writing. At the molecular scale, the process relies on nitroxide-mediated photopolymerization (NMP2) triggered by a light-sensitive alkoxyamine. In addition to the proof-of-concept and examples of achievable structures, including multichemistry patterns and 3D structures, this paper aims at investigating the physicochemical phenomena involved under such conditions. In particular, the parameters influencing the repolymerization process are considered, and special attention is paid to the study of the impact of oxygen on the spatial control of the polymerization. Such work opens many possibilities towards the fabrication of on-demand high-resolution (multi)functional polymer micro- and nanostructures.