Evolution of plasmon resonances during plasma deposition of silver nanoparticles

In situ real-time spectroscopic ellipsometry is used to monitor the growth of magnetron sputtered silver nanoparticles on SiO2 substrates, through the percolation threshold and into the bulk film regime. The plasmon polariton resonances in the natioparticulate regime are effectively modelled by a Lorentz oscillator. The resonance energy of the oscillator is observed to reduce to zero shortly after the percolation threshold, whereby the oscillation is described by Drude free electron theory. From the Drude theory, the electronic mean free path is observed to increase dramatically at the percolation threshold, to a value of 16 nm in the bulk regime, in good agreement with x-ray diffraction and transmission electron microscope measurements of the crystallite size in the films. Shortly before the percolation threshold the data is better modelled by two Lorentz oscillators, attributed to coupling between the plasmon polaritons. The onset of the coupling is determined to occur at a surface area coverage of 52%.