Abstract
The hysteresis phenomenon in a polymer thin film transistor (PTFT) with either poly(3‐hexylthiophene), poly(3‐dodecylthiophene), or poly[2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐phenylene vinylene] is investigated over a wide range of temperatures, and found to be generated by the delay in main chain ring distortion with an applied electric field. In the temperature range for side chain relaxation, main chain motion induced by side chain motion already starts such that polarization of the main chain by the applied electric field is permitted but in a limited extent and is not in phase with the variation in electric field. In the main chain relaxation temperature range, the extent of segmental motion increases, which leads to the main chain being more realignable by the applied electric field and thus a reduced hysteresis. After main chain relaxation is complete, the ring can distort more freely and chain segments are able to realign in phase with the applied electric field, which leads to a leveling off of the hysteresis. This investigation shows for first time that the chain relaxation in conjugated polymers is the origin of the hysteresis in PTFT devices.