Nanowire Architectures Improve Ion Uptake Kinetics in Conjugated Polymer Electrochemical Transistors

Organic electrochemical transistors are believed to face an inherent material design tension between optimizing for ion mobility and for electronic mobility. These devices transduce ion uptake into electrical current, thereby requiring high ion mobility for efficient electrochemical doping and rapid turn-on kinetics and high electronic mobility for the maximum transconductance. Here, we explore a facile route to improve operational kinetics and volumetric capacitance in a high-mobility conjugated polymer (poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno [3,2-b]thiophene)], DPP-DTT) by employing a nanowire morphology. For equivalent thicknesses, the DPP-DTT nanowire films exhibit consistently faster kinetics (∼6-10× faster) compared to a neat DPP-DTT film. The nanowire architectures show ∼4× higher volumetric capacitance, increasing from 7.1 to 27.7 F/cm³, consistent with the porous structure better enabling ion uptake throughout the film. The nanowires also exhibit a small but energetically favorable shift in a threshold voltage of ∼17 mV, making the nanostructured system both faster and energetically easier to electrochemically dope compared to neat films. We explain the variation using two atomic force microscopy methods: in situ electrochemical strain microscopy and nanoinfrared imaging via photoinduced force microscopy. These data show that the nanowire film's structure allows greater swelling and ion uptake throughout the active layer, indicating that the nanowire architecture exhibits volumetric operation, whereas the neat film is largely operating via the field effect. We propose that for higher-mobility materials, casting the active layer in a nanowire form may offer faster kinetics, enhanced volumetric capacitance, and possibly lower threshold voltage while maintaining desirable device performance.