Selective Silver Nanocluster Metallization on Conjugated Diblock Copolymer Templates for Sensing and Photovoltaic Applications

Polymer–metal composite films with nanostructured metal and/or polymer interfaces show a significant perspective for optoelectronic applications, for example, as sensors or in organic photovoltaics (OPVs). The polymer components used in these devices are mostly nanostructured conductive polymers with conjugated π-electron systems. Enhanced OPV’s power conversion efficiencies or sensor sensitivity can be achieved by selective metal deposition on or into polymer templates. In this study, we exploit time-resolved grazing-incidence X-ray scattering to observe the metal–polymer interface formation and the cluster crystallite size in situ during silver (Ag) sputter deposition on a poly(3-hexylthiophene-2,5-diyl)-b-poly(methyl methacrylate) (PMMA-b-P3HT) template. We compare the arising nanoscale morphologies with electronic properties, determine Ag growth regimes, and quantify the selective Ag growth for the diblock copolymer (DBC) template using the corresponding homopolymer thin films (P3HT and PMMA) as a reference. Hence, we are able to describe the influence of the respective polymer blocks and substrate effects on the Ag cluster percolation: the percolation threshold is correlated with the insulator-to-metal transition measured in situ with resistance measurements during the sputter deposition. The Ag cluster percolation on PMMA-b-P3HT starts already on the network of the hexagonal P3HT domain before a complete metal film covers the polymer surface, which is complemented by microscopic measurements. In general, this study demonstrates a possible method for the selective Ag growth as a scaffold for electrode preparation in nanoelectronics and for energy harvesting applications.