摘要： Nonfullerene all-small-molecule organic solar cells (NFSM-OSCs) have shown a promising potential towards the commercialization of OSCs, owing to their unique advantages of high purity, easy synthesis and good reproducibility. However, great challenges in the modulation of phase separation morphology have limited their future development. Herein, two novel small molecular donors of BTEC-1F and BTEC-2F, derived from the small molecule DCAO3TBDTT, were designed and synthesized. While using Y6 as the acceptor, the devices based on non-fluorinated DCAO3TBDTT showed an open circuit voltage (Voc) of 0.804 V and a power conversion efficiency (PCE) of 10.64%. Mono-fluorinated BTEC-1F showed an increased Voc of 0.870 V and a PCE of 11.33%. More impressively, the fill factor (FF) of di-fluorinated BTEC-2F based NFSM-OSC was largely improved to 72.35% resulting in an impressive PCE of 13.34%, which was much higher than that of BTEC-1F (61.35%) and DCAO3TBDTT (60.95%). To the best of our knowledge, this is the highest reported PCE to date for NFSM-OSCs. BTEC-2F depicted a more compact molecular stacking and a lower crystallinity as revealed from characterization studies, which was beneficial for enhancing phase separation and carrier transport. Those results demonstrated an effective strategy to improve the performance of NFSM-OSCs via fluorination of small molecular donors and modulation of crystallinity deviation between donors and acceptors.