Toward Efficient All-Polymer Solar Cells via Halogenation on Polymer Acceptors.

Although halogenation has been widely regarded as an effective approach to adjust the properties of organic semiconductors, systematic investigation on the comparison of nonhalogenated and halogenated polymer acceptors only received minor attention in all-polymer solar cell (all-PSC) community. Herein, we report three IDIC-based narrow band gap polymer acceptors, PIDIC2T, PIDIC2T2F, and PIDIC2T2Cl, which are composed of IDIC-C16 building blocks as acceptor units, linking pristine bithiophene, fluorinated bithiophene, or chlorinated bithiophene as donor units. Although these three polymer acceptors exhibit nearly identical lowest unoccupied molecular orbital (LUMO) levels of ca. -3.87 eV with a similar optical band gap of ca. 1.54 eV, we found that different halogen species significantly affect the electron mobility and thin-film morphology of the polymer acceptors. All-PSCs were fabricated by pairing three polymer acceptors with a PBDB-T polymer donor, while PIDIC2T2Cl delivered a highest power conversion efficiency (PCE) of 5.34% due to its favorable bulk morphology with smaller root-mean-square (rms) roughness values, which induce the relatively more balanced charge carrier mobilities. By blending the fluorinated analogue of PBDB-T, PM6, further improved VOC, JSC, and fill factor (FF) of devices were achieved (5.46% for PM6:PIDIC2T, 4.96% for PM6:PIDIC2T2F, 7.11% for PM6:PIDIC2T2Cl), which can be due to the synergistic effect of the deeper highest occupied molecular orbital (HOMO) energy level of PM6, enhanced crystallinity, and more matched charge transport. This systematic study provides an insight into the influence of halogenation (fluorination and chlorination) on the optoelectrical properties of n-type organic semiconductors and demonstrates an efficient strategy that the design guideline for polymer acceptors can be enriched by backbone halogenation to further develop high-performance all-PSCs.