Polymer-Chain Aggregation-induced Electrical Gating at the H- and J-aggregate P3HT

Abstract

This research explores how aggregation influences the electrical behavior at both the planar - heterojunction poly(3-hexylthiophene) (P3HT)/SiO2 and P3HT/ZnO nanocrystal (NC) interfaces. The formation of H- and J-type aggregates leads to distinct molecular ordering and packing structures, manifesting as changes in threshold voltage shifts (electrical gating) as well as absorption and luminescence properties. Ultrasound irradiation (sonication) significantly alters the molecular arrangement in P3HT, favoring the formation of H-aggregates over the typically formed J-aggregates. In pristine P3HT, J-aggregates facilitate efficient exciton movement and electrical generation, resulting in higher photocurrents compared to sonicated-P3HT, which predominantly forms H-aggregates. Field-effect transistors (FETs) based on sonicated P3HT exhibit a more positive threshold voltage and increased mobility, indicating the presence of more mobile charge carriers, even in the absence of an applied voltage. In interfaces with ZnO NC, pristine P3HT demonstrates a considerable shift in threshold voltage under illumination, attributed to electron trapping. Conversely, sonicated P3HT interfaced with ZnO NC shows less electron trapping and minimal change in threshold voltage. This study underscores how the type of aggregate (H or J) in P3HT significantly dictates light-induced electrical gating. Ultrasound irradiation (sonication), while enhancing mobility by improving crystallinity, leads to a decrease in photocurrent efficiency in H-aggregates compared to the J-aggregates present in pristine-P3HT.