On the basis of naphthalene diimide (NDI) units connected to thiophene (T), thienothiophene (TT), or dithienothiophene (DTT) units via a thiophene π-bridge, three new copolymers-PDTNDI-T, PDTNDI-TT, and PDTNDI-DTT, respectively-were synthesized and used in the fabrication of all-polymer solar cells (all-PSCs). The relationships between the structures of the polymers and their optoelectronic properties and photovoltaic performances as electron acceptors in all-PSCs were investigated in detail. As the number of copolymerized heteroaromatic rings in the DTNDI-based polymers increased, the power conversion efficiencies of the resulting all-PSCs were found to decrease. This decreasing trend in the photovoltaic performance is opposite to the results reported previously for NDI-based polymers lacking the thiophene π-bridge and naphthodithiophene diimide-based polymers. In addition, the three polymers were found to exhibit distinct molecular orientations: a face-on orientation for PDTNDI-T and edge-on orientations for PDTNDI-TT and PDTNDI-DTT. Our results indicate that large fused aromatic rings are not necessarily advantageous in the design of NDI-based polymers containing π-conjugated bridges.
Keywords: all-polymer solar cell (all-PSC); dithienothiophene (DTT); naphthalene diimide (NDI); nonfullerene acceptor; thienothiophene (TT).