Alkyl chain modification strategies in both organic semiconductors
and inorganic dielectrics play a crucial role in improving the performance
of organic thin-film transistors (OTFTs). Polyimide (PI) and its derivatives
have received extensive attention as dielectrics for application in
OTFTs because of flexibility, high-temperature resistance, and low
cost. However, low-temperature solution processing PI-based gate dielectric
for flexible OTFTs with high mobility, low operating voltage, and
high operational stability remains an enormous challenge. Furthermore,
even though di-n-decyldinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (C10-DNTT) is known to have very
high mobility as an air-stable and high-performance organic semiconductor,
the C10-DNTT-based TFTs on the PI gate dielectrics still
showed relatively low mobility. Here, inspired by alkyl side chain
engineering, we design and synthesize a series of PI materials with
different alkyl side chain lengths and systematically investigate
the PI surface properties and the evolution of organic semiconductor
morphology deposited on PI surfaces during the variation of alkyl
side chain lengths. It is found that the alkyl side chain length has
a critical influence on the PI surface properties, as well as the
grain size and molecular orientation of semiconductors. Good field-effect
characteristics are obtained with high mobilities (up to 1.05 and
5.22 cm2/Vs, which are some of the best values reported
to date), relatively low operating voltage, hysteresis-free behavior,
and high operational stability in OTFTs. These results suggest that
the strategy of optimizing alkyl side-chain lengths opens up a new
research avenue for tuning semiconductor growth to enable high mobility
and outstanding operational stability of PI-based OTFTs.