Diimide-functionalized arylenes are widely used as n-channel small-molecule semiconductors for applications in organic thin-film transistors and solar cells. Recently, they have been demonstrated to be attractive electron acceptor units for creating high-performance polymer semiconductors with fine tuned bandgaps and frontier molecular orbitals as well as desired film microstructures and morphologies of the resulting polymers.  

　　Here, we present the imide-functionalized polymer semiconductors for applications in high-performance organic thin-film transistors and solar cells. The imide-functionalized aryenes include naphthalene diimide, phthalimide, thiophene imide, and bithiophene imide. By copolymerizing with various electron donor counits, we are able to achieve polymer semiconductors with tunable charge carrier polarities (n-channel, p-channel, and ambipolar). The n-channel polymers show electron mobilities approaching 0.3 cm²/Vs, and p-channel polymers exhibit hole mobilities around 2 cm²/V. The inkjet-patterned polymeric CMOS inverters show voltage gains of 40. The substantial charge carrier mobilities, small bandgaps, and low-lying HOMOs enable the imide-functionalized polymers as excellent electron donor layer in organic solar cells. The solar cells show promising power conversion efficiencies with interesting device performance parameters. Bulk heterojunction organic solar cells show unprecedented fill factors of 75-80%, which greatly boost the power conversion efficiency to 8.7% using polymers with moderate bandgap of ~1.80 eV. The physical origins of such high fill factors have been elucidated and the structure-property-device performance correlations of these polymers have been established.