Structure-Function Correlations in Sputter Deposited Gold/Fluorocarbon Multilayers for Tuning Optical Response

A new strategy to nanoengineer gold/fluorocarbon multilayer (ML) nanostructures is reported. We have investigated the morphological changes occurring at the metal-polymer interface in ML structures with varying volume fraction of gold (Au) and the kinetic growth aspect of the microscale properties of nano-sized Au in plasma polymer fluorocarbon (PPFC). Investigations were carried out at various temperatures and annealing times by means of grazing incidence small-angle and wide-angle X-ray scattering (GISAXS and GIWAXS). We have fabricated a series of MLs with varying volume fraction (0.12, 0.27, 0.38) of Au and bilayer periodicity in ML structure. They show an interesting granular structure consisting of nearly spherical nanoparticles within the polymer layer. The nanoparticle (NP) morphology changes due to the collective effects of NPs diffusion within ensembles in the in-plane vicinity and interlayer with increasing temperature. The in-plane NPs size distinctly increases with increasing temperature. The NPs become more spherical, thus reducing the surface energy. Linear growth of NPs with temperature and time shows diffusion-controlled growth of NPs in the ML structure. The structural stability of the multilayer is controlled by the volume ratio of the metal in polymer. At room temperature, UV-Vis shows a blue shift of the plasmon peak from 560 nm in ML Au/PTFE_1 to 437 nm in Au/PTFE_3. We have identified the fabrication and postdeposition annealing conditions to limit the local surface plasmon resonance (LSPR) shift from Δ λ L S P R = 180 nm (Au/PTFE_1) to Δ λ L S P R = 67 nm (Au/PTFE_3 ML)) and their optical response over a wide visible wavelength range. A variation in the dielectric constant of the polymer in presence of varying Au inclusion is found to be a possible factor affecting the LSPR frequency. Our findings may provide insights in nanoengineering of ML structure that can be useful to systematically control the growth of NPs in polymer matrix.