Interplaying Role of Particle Size and Polymer Layer Thickness on the Large Tunable Optical Response of Polymer-coated Silver Nanostructures

The interplaying role of particle size and polymer layer thickness on the tunable optical response of polymer-coated Ag nanoparticles (NPs) has been studied experimentally and theoretically. A large redshift ( ∼ 38 nm) of surface plasmon resonance (SPR) peak position has been observed experimentally for Ag NPs of sizes in the range of 8−18 nm synthesized by polyol process with the varying concentration of metal precursor (AgNO 3 ) and using a surfactant (PVP) as a stabilizer. The observed large redshift of the SPR peak position of Ag NPs coated with PVP has been argued due to mainly change of NP size as well as change of local dielectric environment in the vicinity of the Ag NPs. The experimentally observed SPR peak shift has been explained by considering the system as a metal-core polymer-shell nanostructure. The change of local dielectric environment of the surrounding of the NPs is due to the change in the PVP layer on the NPs. Such observation has been confirmed through the theoretical studies considering the changes of NP size as well as the effective thickness of the PVP layers on the NPs. The SPR peak of the system with core-shell nanostructure has been found to vary linearly with the increase in radius of core and thickness of shell together. However, it changes exponentially with particle size alone. It has been found from a detailed study that the change in the ratio of radius of core and thickness of the shell is responsible for the observed redshift. Thus, the redshift of SPR peak position of Ag NPs cannot be justified by only considering the increase in particle size. Rather shell thickness has been found to play a prominent role in the SPR peak shift. This study can be used to understand the optical response of noble metal NPs coated with organic polymers.