Deformation induced evolution of plasmonic responses in polymer grafted nanoparticle thin films.

Abstract

Multi-functional nanoparticle thin films are being used in various applications ranging from biosensing to photo-voltaics. In this study, we integrate two different numerical approaches to understand the interplay between the mechanical deformation and optical response of polymer grafted plasmonic nanoparticle (PGPN) arrays. Using numerical simulations we examine the deformation of thin films formed by end-functionalised polymer grafted nanoparticles subject to uniaxial elongation. The induced deformation causes the particles in the thin film network to rearrange their positions by two different mechanisms viz. sliding and packing. In sliding, the particles move in the direction of induced deformation. On the other hand, in packing, the particles move in a direction normal to that of the induced deformation. By employing a Green's tensor formulation in polarizable backgrounds for evaluating the optical response of the nanoparticle network, we calculate the evolution of the plasmonic response of the structure as a function of strain. The results indicate that the evolution of plasmonic response closely follows the deformation. In particular, we show that the onset of relative electric field enhancement of the optical response occurs when there is significant rearrangement of the constituent PGPNs in the array. Furthermore, we show that depending on the local packing/sliding and the polarization of the incident light there can be both enhancement and suppression of the SERS response.