Abstract
We report the synthesis of a linear-type dibromocarbazoledioxazine (CZ) derivative as a new precursor for semiconducting polymers. The chemical structures of the CZ unit and its polymers with thiophene or thienothiophene spacers (namely, PCZT and PCZTT) were fully characterized. PCZT and PCZTT possessed similar medium optical band gap (E opt g) and electrochemical band gap (E cv g) of around 1.70 eV estimated from the onset absorption and electrochemical redox potentials of the thin films, respectively. Computational density functional theory (DFT) calculations suggested that the backbone of the PCZT might be highly twisted, while that of PCZTT could be very planar. The effect of different backbone geometries on the charge-transport properties was studied by using thin film transistors (TFTs). The TFT device based on PCZTT showed a four times higher hole mobility as compared to that based on PCZT. The superior TFT performances of PCZTT were reasonably attributed to its edge-on backbone packing orientations toward the Si substrate revealed by the grazing-incidence wide-angle X-ray scattering (GIWAXS), which was favorable for in-plane charge transport in the TFT devices.