Transition from out-of-plane to in-plane contribution for the optical second harmonic generation response from a silver metallic nanoparticle film

The time evolution of the second harmonic generation (SHG) intensity during the formation of a silver spherical nanoparticle film at the water/1,2-dichloroethane interface is reported. The 5 nm diameter silver nanoparticles were initially dispersed in the water phase and their precipitation at the interface was triggered with the addition of sodium chloride. The time evolution of the SHG intensity exhibited two distinct regimes. First, an intensity increase was observed during the film formation with the deposition and the reorganization of the nanoparticles at the interface. Then, a slow decrease of the intensity due to rearrangements within the film was observed. Polarization-resolved experiments were also performed and showed that the initial dominant out-of-plane contribution of the quadratic nonlinearity underwent a reorientational change towards a dominant in-plane contribution associated with a smoother but still discontinuous metallic film.