Thin polymer films made of conjugated polymers are promissing for fabrication of photovoltaic, thermoelectric or sensing devices. A proper ordering of the chains should influence the performance of such systems, which may take advantages of anisotropy offered by the stretched polymer chains in surface-grafted polymer brushes. However, synthesis of such conjugated brushes is challenging since there are no versatile controlled polymerization techniques easily applicable for that purpose.<br/>We have introduced self-templating surface-initiated polymerization leading to formation of ladder-like brushes with one chain in a pair being conjugated. The brushes were synthesized using the two-step procedure that combines surface-initiated controlled radical polymerizations of bifunctional monomers followed by the polymerization of the pendant groups leading to conjugated chains (e.g. polythiophene, polyacetylene). The pendant groups, before the second polymerization step, were prealigned along the stretched chains in densely grafted brushes. The brushes after doping exhibited high conductivity in the direction perpendicular to the surface as showed using conductive atomic force microscopy. Importantly, conjugated polymer brushes based on e.g. poly(acetylene) and poly(thiophene) with such ladder-like architecture were also shown to exhibit long term stability in air as compared to appropriate polymer films. Additionally, a novel mixed self-doping (conjugated/polyelectrolyte) brushes were prepared and their structure was studied using spectroscopic and microscopic methods (AFM, nano-FTIR, XPS profiling). The ladder-like architecture of the brushes was found to ensure long conjugation length at a high grafting density of the conjugated chains that is necessary for the fabrication of highly oriented and stable platforms of molecular wires

Self-templating surface-initiated polymerization for fabrication of conjugated polymer brushes

2019 Fall National Meeting

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