CO₂ Responsive Thin-Film Transistors Using Conjugated Polymer Complexes with Single-Walled Carbon Nanotubes

Introduction of amidine groups within the side chains of a conjugated polyfluorene was carried out using copper-catalyzed azide-alkyne cycloaddition. The resulting polymer was shown to form strong supramolecular interactions with the sidewalls of single-walled carbon nanotubes (SWNTs), forming polymer-nanotube complexes that exhibited solubility in various organic solvents. It was shown that the polymer-SWNT complexes were responsive to CO₂, where the amidine groups formed amidinium bicarbonate salts upon CO₂ exposure, causing the polymer-SWNT complexes to precipitate. This reaction could be reversed by bubbling N₂ through the solution, which caused the polymer-SWNT complexes to redissolve. Incorporation of the polymer-SWNT complexes within thin-film transistor (TFT) devices as the active layer resulted in a CO₂-responsive TFT sensor. It was found that the sensory device underwent a reversible shift in its threshold voltage from 5 to -1 V as well as a 1 order of magnitude decrease in its on-current upon exposure to CO₂. This work shows that conjugated polymer-wrapped SWNTs having sensory elements within the polymer side chain can be used as the active layer within functional SWNT-based TFT sensors.