Two new donor-acceptor polymers containing benzo[2,1-b:3,4-b':5,6-c'']trithiophene (BTT) as donor and diketopyrrolopyrrole (DPP) as acceptor are synthesized and applied in OFETs. By tuning the alkyl substituents of the polymers, a striking difference in packing order, thin-film arrangement, and charge carrier transport is observed. The polymer without substituents at the BTT exhibits a hole mobility two orders of magnitude higher than that with alkyl chains therein.
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