Synthesizing copolymer acceptors based on a mix of three co-monomers is a facile and effective strategy to control the aggregation and crystallinity of semiconducting polymers which has been exploited to improve the photovoltaic performance of all-polymer solar cells (all-PSCs). Applying this strategy to the well-studied electron-transporting polymer acceptor PNDI2OD-T2, different amounts of 3-octylthiophene (OT) are used to partially replace the bithiophene (T2) unit, resulting in three copolymer acceptors PNDI-OTx where x = 5, 10, or 15%. Another polymer, namely PNDI2OD-C8T2, consisting of naphthalene diimide (NDI) polymerized with 3-octyl-2,2′-bithiophene (C8T2) is also synthesized for comparison. It is found that the solution aggregation and thin-film crystallinity of PNDI-OTx are systematically tuned by varying x, evidenced by temperature-dependent UV-vis and grazing incidence wide-angle X-ray scattering measurements. PNDI2OD-C8T2 is also found to have reduced solution aggregation and thin-film crystallinity relative to PNDI2OD-T2. However, the photovoltaic performance of all-PSCs based on J71:PNDI-OTx and J71:PNDI2OD-C8T2 blends are much lower than that of the reference J71:PNDI2OD-T2 system. Extensive morphological studies indicate that reduced aggregation and crystallinity do not guarantee a more favorable blend morphology, with coarser phase separation found in J71:PNDI-OTx and J71:PNDI2OD-C8T2 blends compared to J71:PNDI2OD-T2 blends. Furthermore, the OT-modified copolymers with reduced crystallinity are found to have reduced electron mobilities. The results here suggest that reduced aggregation and less crystallinity of random copolymer acceptors do not always produce favorable morphology in polymer/polymer blends and do not guarantee for improvement in the photovoltaic performance.
- copolymer acceptors
- ll-polymer solar cells