Effect of Donor Building Blocks on the Charge-Transfer Characteristics of Diketopyrrolopyrrole-Based Donor-Acceptor-Type Semiconducting Copolymers.

We investigate the effect of donor (D) building blocks on the charge transportation characteristics of donor (D)-acceptor (A)-type semiconducting copolymers with alternating electron-donating and electron-accepting units to provide a basis for the rational design of high-performance semiconducting polymers. For this purpose, we studied three different diketopyrrolopyrrole (DPP)-based semiconducting copolymers comprising a common dithienyl-DPP [3,6-dithienyl-2,5-diketopyrrolo(3,4-c)pyrrole] and variable donor moieties: phenylene (P)-PDPPTPT, thiophene (T)-PDPP3T, and thienothiophene (TT)-PDPP2T-TT. Structural analysis using grazing incidence X-ray diffraction indicates that all three DPP-based copolymer films have edge-on phases but poor crystallinity of the films, except the PDPP2T-TT copolymer with branched alkyl side chains that are relatively long. The electrical measurements show that the DPP-based copolymer with a TT donor unit has the highest field-effect mobility value of 0.30 cm2/V s. To understand the role of the donor units in DPP-based D-A copolymers, further insight into the charge transportation behavior is realized by analyzing the temperature-dependent transfer curves of the DPP semiconducting copolymer-based field-effect transistors using the Gaussian disorder model. Compared to the DPP-based D-A-type semiconducting copolymer with a P-moiety and shorter-branched alkyl side chains that exhibit a broad distribution in the density of localized states (DOS) and a higher thermal-activated energy for charge hopping, the DPP copolymers with a TT-moiety and longer branched side chains have the narrowest DOS, the lowest activation energy, and thus the highest hole mobility. These results suggest that the higher mobilities obtained from PDPP2T-TT with a TT donor unit can be attributed to the suppressed DOS distribution near the transport level, which mainly originates from the narrowest energy band gap tuned with the orbital couplings of the DPP acceptor and TT donor units.