Tunable Charge Transport Using Supramolecular Self-Assembly of Nanostructured Crystalline Block Copolymers

Electronically functionalized block copolymers, combining covalently linked p-type and n-type blocks, show switching behavior of charge transport in organic field effect transistors (OFETs). The electronically active subunits self-assemble into continuous microdomains in a nanoscale regime, thereby forming percolation channels for holes or electrons or both depending on the composition and processing conditions. Here, we establish a charge transport-morphology relation for donor-acceptor block copolymers with two crystalline blocks. The n-type and p-type blocks self-assemble into two-dimensional lattices of π-π stacks and main chain polymer lamellae, respectively, over a broad composition range. Controlling the crystallization preferences of the two blocks by thermal annealing allows controlling the OFET polarity. Depending on the block ratio, the charge transport can be tuned from p-type to n-type or p-type to ambipolar, respectively. The impact of nanostructured phase separation is further delineated by X-ray diffraction, time-resolved spectroscopy, and scanning electron microscopy studies.