Pyromellitic Diimide–Ethynylene-Based Homopolymer Film as an N-Channel Organic Field-Effect Transistor Semiconductor

We report the synthesis and characterization of two solution-processable pyromellitic diimide (PyDI)-acetylene-based conjugated homopolymers. Adjacent PyDI cores were connected with triple bond linkages by reacting 3,6-dibromo- N, N ′-dialkyl pyromellitic diimides with bis(tributylstannyl)acetylene under Stille coupling conditions. Cyclic voltammetry revealed that these polymers have sufficient electron affinity to accept electrons. Absorption spectra revealed that one polymer, with a simple octyl chain, has greater intermolecular interaction or conjugation after forming a thin film, and that film exhibited electron transport in top-gate bottom-contact mode organic field-effect transistor (OFET) devices. X-ray diffraction (XRD) and atomic force microscopy (AFM) results show that the octyl polymer is amorphous on the bulk scale. The polymer exhibited electron mobility of about 2 × 10 –4 cm 2 V –1 s –1 with on/off ratio of 10 3 and is the simplest n-channel polymer yet reported. A 4-trifluoromethylphenethyl side chain did not result in measurable electron mobility. The octyl polymer exhibited negative Seebeck coefficient on the order of −40 μV/K in thermoelectric devices, further substantiating its n-channel activity. The demonstration of electron transport from such a simple polymer has opened a new path for obtaining n-channel semiconducting activity from polymer films.