Tunable gap plasmons in gold nanospheres adsorbed into a pH-responsive polymer film

Plasmon nanorulers are exquisitely sensitive distance sensors that are based on the electromagnetic interaction between metal nanoparticles and surfaces. We hypothesize that nanorulers can act as quantitative probes of processes such as particle aggregation and adsorption, and deploy them to investigate particle adsorption onto stimulus-responsive polymer films. While such systems have previously been qualitatively investigated with plasmon nanorulers, our quantitative analysis should provide deeper insights.

Gold nanospheres are adsorbed from solution onto pH-responsive, amine-rich polyelectrolyte multilayer (PEM) films that are either directly deposited on a gold substrate or onto an intermediate self-assembled monolayer (SAM) of charged thiols. Fitting the optical scattering spectrum to a full-wave calculation, we quantify the sphere-substrate gap distance with good accuracy.

We find that the gold spheres partially embed into the PEMs rather than ride on top of them, and that although the amount of actuation of the spheres afforded by tuning the pH is well controlled, it is significantly smaller than the corresponding thickness changes in unstrained films. Further, the presence of a SAM below the PEM increases the amount of polymer in the PEM, except for the thickest and most highly charged films, where the SAM instead appears to displace from the area below the nanospheres.