Ladder‐Like Difluoroindacenodithiophene‐4,9‐dione Derivative: A New Acceptor System for High‐Mobility n‐Type Polymer Semiconductors

Abstract Ladder‐like aromatic diketones (LADK), which possess a coplanar π‐extended geometry, a high electron deficiency as well as various attractive optoelectronic properties, are demonstrated as the promising candidates in building small‐molecule organic electron‐transporting materials, yet reports on direct integration of these structural motifs into n‐type polymers are rarely accessed. Herein, it is demonstrated that a possibility of realizing unipolar n‐type characteristics of such acceptor system by developing two novel donor–acceptor type polymers, in which the newly developed LADK unit, named as 3,8‐bis(2‐decyltetradecyl)‐5,10‐difluoro‐ s ‐indaceno[1,2‐ b :5,6‐ b ′]dithiophene‐4,9‐dione (FIDTO‐R), is adopted as the acceptor segments. The resulting polymers present deep‐lying unoccupied molecular orbital levels (as low as −3.84 eV), compact π–π stacking ( d ‐spacing, ≈3.57 Å) coupled with uniform nanofiber‐like surface morphology. All these factors contribute to excellent unipolar n‐type characteristics with high electron mobilities of 0.27 and 1.01 cm 2 V −1 s −1 , together with high inverter gain values of 141 and 80, respectively. The recorded values are among the best in n‐type polymer field‐effect transistors and associated inverter circuits. These findings unambiguously reveal that the as‐prepared FIDTO‐R and its analog LADK derivatives are another type of excellent building blocks for the construction of high‐mobility n‐type polymers.