Inducing the self-assembly of π-conjugated polymers into semicrystalline aggregates has been a topic of substantial interest in the field of organic electronics and is typically achieved using energy-intensive solution processing or postfilm deposition methods. Here, we demonstrate the ability of bioderived cellulose nanocrystals (CNCs) to act as structure-directing agents for the conjugated semiconducting polymer, poly(3-hexylthiophene) (P3HT). CNCs were grafted with polystyrene, P3HT or poly(N-isopropylacrylamide), and subsequently blended with P3HT in solution to study the effect on conjugated polymer self-assembly. The presence of polymer-grafted CNCs resulted in an increase in P3HT semicrystalline aggregate formation, the degree of which depended on the surface free energy of the grafted polymer. The time-dependent P3HT aggregation was characterized by UV-vis spectroscopy, and the resulting data was fit to the Avrami crystallization model. The surface energies of each additive were calculated via contact angle measurements and were used to elucidate the mechanism of P3HT aggregation in these blended systems. P3HT aggregation was enhanced by unfavorable polymer-polymer interactions at the CNC surface, and spatial confinement effects that were imposed by phase separation. Finally, films were cast from the P3HT/CNC solutions and their electronic performance was characterized by organic field-effect transistor device measurements. Films containing polymer-grafted CNCs exhibited higher charge-carrier mobilities, in some cases, up to a 6-fold increase. These bioderived particles constituted a significant volume fraction of the deposited P3HT thin films with an increase in performance, showing promise as a method for reducing costs and improving the sustainability of organic electronics.
Keywords: OFET devices; SI-ATRP; cellulose nanocrystals; conjugated polymers; crystallization.