High performance thin film transistors based on bi-thieno[3,4-c]pyrrole-4,6-dione-containing copolymers: tuning the face-on and edge-on packing orientations

Abstract

Bi-thieno[3,4-c]pyrrole-4,6-dione (bi-TPD) and oligothiophene copolymer semiconductors P1–P4, with different alkyl side chain densities and orientations, were synthesized. Their physicochemical properties were systematically characterized. With trimethoxy(octadecyl)silane (OTMS) modified SiO₂ as substrates, the as-spun thin films of P1, P3 and P4 adopted the face-on packing structure while the P2 films displayed the edge-on packing arrangement. The packing differences of P1–P4 were ascribed to their different alkyl chain densities and orientations. The higher alkyl chain density is favorable to the face-on packing structure. After thermal annealing, the packing orientation of P2 remained and the packing structures of P1, P3 and P4 changed. P1 and P4 based films exhibited the coexistence of the edge-on and face-on packing structures in which the edge-on structure was predominant, and P3 based thin films were converted to the edge-on packing arrangement. The relationship between the aggregation structures and charge carrier transport properties of these films was explored through thin film transistors. All devices exhibited p-channel behavior with a maximum mobility larger than 1.0 cm² V⁻¹ s⁻¹. Interestingly, the P3 films with face-on packing structures displayed a high mobility up to 1.18 cm² V⁻¹ s⁻¹ (average mobility of 1.02 cm² V⁻¹ s⁻¹), very close to the edge-on packed films which showed a maximum mobility of 1.4 cm² V⁻¹ s⁻¹ (average mobility of 1.16 cm² V⁻¹ s⁻¹). These results demonstrated, similar to edge-on packing structures, the face-on packing arrangement with π–π interactions facilitated charge carrier transport.