Although state-of-the-art ambipolar polymer semiconductors have been extensively reported in recent years, highperformance ambipolar polymers with tunable dominant polarity are still required to realize on-demand, target-specific, high-performance organic circuitry. Herein, dithienyl-diketopyrrolopyrrole (TDPP)-based polymer semiconductors with engineered side-chains have been synthesized, characterized and employed in ambipolar organic field-effect transistors, in order to achieve controllable and improved electrical properties. Thermally removable tert-butoxycarbonyl (t-BOC) groups and hybrid siloxane-solubilizing groups are introduced as the solubilizing groups, and they are found to enable the tunable dominant polarity and the enhanced ambipolar performance, respectively. Such outstanding performance based on our molecular design strategies makes these ambipolar polymer semiconductors highly promising for low-cost, large-area, and flexible electronics.
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