Solution-based electrical doping of semiconducting polymer films over a limited depth.

Solution-based electrical doping protocols may allow more versatility in the design of organic electronic devices; yet, controlling the diffusion of dopants in organic semiconductors and their stability has proven challenging. Here we present a solution-based approach for electrical p-doping of films of donor conjugated organic semiconductors and their blends with acceptors over a limited depth with a decay constant of 10-20 nm by post-process immersion into a polyoxometalate solution (phosphomolybdic acid, PMA) in nitromethane. PMA-doped films show increased electrical conductivity and work function, reduced solubility in the processing solvent, and improved photo-oxidative stability in air. This approach is applicable to a variety of organic semiconductors used in photovoltaics and field-effect transistors. PMA doping over a limited depth of bulk heterojunction polymeric films, in which amine-containing polymers were mixed in the solution used for film formation, enables single-layer organic photovoltaic devices, processed at room temperature, with power conversion efficiencies up to 5.9 ± 0.2% and stable performance on shelf-lifetime studies at 60 °C for at least 280 h.

Simultaneous cross-linking and p-doping of a polymeric semiconductor film by immersion into a phosphomolybdic acid solution for use in organic solar cells.

Poly[N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT) is shown to be simultaneously cross-linked and p-doped when immersed into a phosphomolybdic acid solution, yielding conductive films with low solubility that can withstand the solution processing of subsequent photoactive layers. Such a modified PCDTBT film serves to improve hole collection and limit carrier recombination in organic solar cells.