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Silver nanoparticle films were deposited by sputtering at room temperature and were annealed while monitoring by real time spectroscopic ellipsometry (SE). The nanoparticle dielectric functions (0.75 eV–6.5 eV) obtained by SE were modeled using Lorentz and generalized oscillators for the nanoparticle plasmon polariton (NPP) and interband transitions, respectively. The nanoparticle melting point could be identified from variations in the oscillator parameters during annealing, and this identification was further confirmed after cooling through significant, irreversible changes in these parameters relative to the as-deposited film. The variation in melting point with physical thickness, and thus average nanoparticle diameter, as measured by SE enables calculation of the surface energy density.