Improvement of poly(3-hexylthiophene-2,5-diyl) electron mobility through complete elimination of regioregularity defects

The improvement of electron transport in polymer semiconductors is highly desirable for realizing robust, large-area and low-cost organic integrated circuits. This work investigates the effect of regioregularity on the intrinsic hole and electron transport characteristics of poly(3-hexylthiophene-2,5-diyl) (P3HT) using current-voltage (I-V) measurements in metal/polymer/metal sandwich structures. Through a direct comparison between 93% regioregular P3HT (EG-P3HT) and 100% regioregular defect-free poly(3-hexylthiophene-2,5-diyl) (DF-P3HT), it is found that the elimination of regioregularity defects improves the electron mobility of DF-P3HT (1.05 × 10-7 cm2 V-1 s-1) by three orders of magnitude compared to the 93% regioregular EG-P3HT sample (1.82 × 10-10 cm2 V-1 s-1). Quantum chemical calculations indicate that the improvement of electron mobility in DF-P3HT can be associated to the lower degree of disorder in these samples that tends to increase the transfer angle between the lowest unoccupied molecular orbitals of adjacent chains. At the same time, the lower dipole moments produced by the defect-free polymer molecules also appears to play an important role in decreasing the susceptibility of charge transport to environment-induced electron traps. The obtained results provide a strong evidence that the elimination of regioregularity defects is an effective technique to improve electron transport and restore the symmetry between hole and electron mobility in P3HT as well as other thiophene-based polymers.