Spectral Degeneracy Breaking of the Plasmon Resonance of Single Metal Nanoparticles by Nanoscale Near-Field Photopolymerization

We report on controlled nanoscale photopolymerization triggered by enhanced near fields of silver nanoparticles excited close to their dipolar plasmon resonance. By anisotropic polymerization, symmetry of the refractive index of the surrounding medium was broken: C∞v symmetry turned to C2v symmetry. This allowed for spectral degeneracy breaking in particles plasmon resonance whose apparent peak became continuously tunable with the incident polarization. From the spectral peak, we deduced the refractive-index ellipsoid fabricated around the particles. In addition to this control of optical properties of metal nanoparticles, this method opens new routes for nanoscale photochemistry and provides a new way of quantification of the magnitude of near fields of localized surface plasmons.