Stability and dewetting of metal nanoparticle filled thin polymer films: control of instability length scale and dynamics

Abstract

We investigate the influence of gold nanoparticle addition on the stability, dewetting, and pattern formation in ultrathin polymer−nanoparticle (NP) composite films by examining the length and time scales of instability, morphology, and dynamics of dewetting. For these 10−50 nm thick (h) polystyrene (PS) thin films containing uncapped gold nanoparticles (diameter 3−4 nm), transitions from complete dewetting to arrested dewetting to absolute stability were observed depending on the concentration of the particles. Experiments show the existence of three distinct stability regimes: regime 1, complete dewetting leading to droplet formation for nanoparticle concentration of 2% (w/w) or below; regime 2, partial dewetting leading to formation of arrested holes for NP concentrations in the range of 3−6%; and regime 3, complete inhibition of dewetting for NP concentrations of 7% and above. Major results are (a) length scale of instability, where λ_H∼hⁿ remains unchanged with NP concentration in regime 1 (n∼2) but increases in regime 2 with a change in the scaling relation (n∼3−3.5); (b) dynamics of instability and dewetting becomes progressively sluggish with an increase in the NP concentration; (c) there are distinct regimes of dewetting velocity at low NP concentrations; (d) force modulation AFM, as well as micro-Raman analysis, shows phase separation and aggregation of the gold nanoparticles within each dewetted polymer droplet leading to the formation of a metal core−polymer shell morphology. The polymer shell could be removed by washing in a selective solvent, thus exposing an array of bare gold nanoparticle aggregates.