The reproducible low-cost fabrication of functional polymer-metal interfaces via self-assembly is of crucial importance in organic electronics and organic photovoltaics. In particular, submonolayer and nanogranular systems expose highly interesting electrical, plasmonic, and catalytic properties. The exploitation of their great potential requires tailoring of the structure on the nanometer scale and below. To obtain full control over the complex nanostructural evolution at the polymer-metal interface, we monitor the evolution of the metallic layer morphology with in situ time-resolved grazing-incidence small-angle X-ray scattering during sputter deposition. We identify the impact of different deposition rates on the growth regimes: the deposition rate affects primarily the nucleation process and the adsorption-mediated growth, whereas rather small effects on diffusion-mediated growth processes are observed. Only at higher rates are initial particle densities higher due to an increasing influence of random nucleation, and an earlier onset of thin film percolation occurs. The obtained results are discussed to identify optimized morphological parameters of the gold cluster ensemble relevant for various applications as a function of the effective layer thickness and deposition rate. Our study opens up new opportunities to improve the fabrication of tailored metal-polymer nanostructures for plasmonic-enhanced applications such as organic photovoltaics and sensors.
Keywords: gold cluster morphology; in situ GISAXS; polymer−metal interfaces; real-time growth kinetics; sputter deposition rates.