Wavelength- and Energy-Dependent Nonlinear Absorption and Transient Absorption in Silver Nanoparticles

Abstract

Nonlinear absorption (NLA) in silver nanoparticles (Ag NPs) is strongly affected by plasmonic field enhancement. However, its wavelength- and energy-dependent evolution on the red side of the surface plasmon resonance (SPR) band remains insufficiently understood. Here, we systematically investigate the NLA properties of Ag NPs using open-aperture (OA) Z-scan measurements combined with femtosecond transient absorption (TA) spectroscopy. The results show that Ag NPs exhibit saturable absorption (SA) under low excitation energies, whereas higher excitation energies induce a mixed SA/reverse saturable absorption (RSA) response. A pronounced wavelength dependence is also observed as the excitation approaches the SPR band, where nonlinear absorption gradually evolves with spectral detuning. TA measurements revealed ultrafast carrier dynamics characterized by a fast electron–phonon relaxation process (~3.3 ps) followed by a slower lattice cooling process (~46 ps). These results demonstrate that the nonlinear response is governed by the interplay between plasmonic resonance and ultrafast carrier relaxation, providing insights for the design of plasmonic nanomaterials for ultrafast nonlinear photonic applications.