Controlling the Microstructure of Conjugated Polymers in High-Mobility Monolayer Transistors via the Dissolution Temperature.

It remains a challenge to precisely tailor the morphology of polymer monolayers to control charge transport. Herein, the effect of the dissolution temperature (Tdis ) is investigated as a powerful strategy for morphology control. Low Tdis values cause extended polymer aggregation in solution and induce larger nanofibrils in a monolayer network with more pronounced π-π stacking. The field-effect mobility of the corresponding monolayer transistors is significantly enhanced by a factor of four compared to devices obtained from high Tdis with a value approaching 1 cm2  V-1  s-1 . Besides that, the solution kinetics reveal a higher growth rate of aggregates at low Tdis , and filtration experiments further confirm that the dependence of the fibril width in monolayers on Tdis is consistent with the aggregate size in solution. The generalizability of the Tdis effect on polymer aggregation is demonstrated using three other conjugated polymer systems. These results open new avenues for the precise control of polymer aggregation for high-mobility monolayer transistors.