On the physical contributions to the third-order nonlinear optical response in plasmonic nanocomposites

Au and Ag isotropic and anisotropic nanocomposites were prepared using the ion implantation technique. Their optical properties were studied at several wavelengths in the optical range 300-800 nm, across their plasmon resonances. The linear regime was characterized by measuring the absorption spectrum and the third-order nonlinear regime by means of the Z-scan technique using a tunable picosecond pulsed laser system (26 ps). Open-aperture Z-scan traces show a superposition of different optical nonlinear absorption (NLA) processes in the whole range studied. We associate these phenomena with the excitation of inter-and intra-band electronic transitions, which contribute with a positive sign to NLA, and to the formation of hot-electrons, which contribute with opposite sign to NLA. Closed-aperture traces for measuring nonlinear refraction (NLR) show different signs for Au and Ag samples, and a change of sign in Au is found when purely inter-band transitions are excited. In this work, for the appropriate wavelength, it is worth remarking on the free-electron response to the exciting light and its strong contribution to the nonlinear optical properties for low (intra-band) and high (hot-electrons) irradiances.