Herein,
we report a series of tetrafluoroethylene (TFE)-containing
semiconducting polymers PNBDO-FDTEm (m = 90, 80, 70, 60, and 0), in which the TFE segments were
first introduced into polymeric main chains as flexible π-nonconjugated
nodes, and its fully conjugated analogue PNBDO-FDTE100. Our results indicate that the TFE segment is quite compatible with
the NBDO-alt-FDTE conjugated matrix system. The HOMO/LUMO
energy levels (approximately −6.0/–4.0 eV) and optical
band gaps (1.28 eV) remain almost the same in the polymers with the
TFE content varying from 0% to 40%. The polymers PNBDO-FDTEm (m = 90, 80, 70, and 60) have
similar highly ordered molecular packing with close π–π
stacking in a thin film as PNBDO-FDTE100 does, implying
that the TFE segments exert no clear negative influences on the molecular
packing of these polymers either. PNBDO-FDTE100 exhibited
a much high electron mobility (μe) of 7.43 cm2 V–1 s–1, while PNBDO-FDTE90 and PNBDO-FDTE80 also showed impressively
high μe values of 7.25 and 6.00 cm2 V–1 s–1, respectively. However, PNBDO-FDTEm (m = 70, 60,
and 0) afforded a μe as low as 0.182 cm2 V–1 s–1. We attributed this
to the transition of the carrier transport mode caused by the increase
in the number of π-nonconjugated nodes.