Surface plasmon mediated harmonically resonant effects on third harmonic generation from Au and CuS nanoparticle films

A growing class of nonlinear materials employ the localized surface plasmonic resonance (LSPR) of nanoparticles to enhance harmonic generation. Material systems containing harmonically coupled metallic and semiconductor plasmonic nanoparticles have been shown to further increase performance. Here, we explore the effect of dual plasmonic interactions in bilayer CuS and Au nanoparticle films on third harmonic generation (THG). Detuning the CuS LSPR away from the excitation frequency changes the dominant upconversion pathway from THG to multiple photon photoluminescence (MPPL). Changing the size of the Au nanoparticle red shifts the LSPR from the second harmonic of the pump frequency and also eliminates the enhancement effect. When both LSPRs satisfy the harmonic condition, simultaneous excitation of CuS-Au nanoparticle films at the resonant frequency of each nanoparticle species enhances the generation of third harmonic light by sum-frequency generation, suggesting that the enhancement of THG in dually plasmonic nanoparticle films is the result of a cascaded nonlinear mechanism. An analytic model of the interaction between the plasmonic nanoparticles due to incoherent dipolar interactions is also presented. Understanding these processes opens a pathway for developing ultrafast, high-efficiency upconversion thin-film devices by clarifying the conditions that efficiently produce third harmonic generation without background MPPL or additional harmonics.