title: Plasmon-based free-radical photopolymerization: effect of diffusion on nanolithography processes.
abstract: This Article interrogates the mechanisms responsible for nanoscale photopolymerization induced by confined and enhanced electromagnetic fields. Surface plasmon dipolar resonance of individual Ag nanoparticles was used as an optical near-field source to locally trigger the reaction of a photopolymerizable formulation. Laser excitation of the nanoparticles embedded in the formulation reproducibly generates polymer features with typical dimensions ranging from 2 nm to a few tens of nanometer. We have determined the physicochemical parameters and mechanisms controlling the spatial extent of the photopolymerization process. We found that the diffusion of the dye is the main process limiting the polymerization reaction, as opposed to what is observed at the microscale with an equivalent chemical system. This approach demonstrates that plasmon-based polymerization can achieve true nanometer scale resolution and also provides a unique opportunity to investigate photochemistry at this length scale.
authors: Laboratoire de Nanotechnologie et d'Instrumentation Optique LNIO-ICD CNRS-UMR 6279, Université de Technologie de Troyes, Troyes, France.
authors: Claire
authors: C
authors: Deeb
authors: Carole
authors: C
authors: Ecoffet
authors: Renaud
authors: R
authors: Bachelot
authors: Jérôme
authors: J
authors: Plain
authors: Alexandre
authors: A
authors: Bouhelier
authors: Olivier
authors: O
authors: Soppera