13.34 % Efficiency Non‐Fullerene All‐Small‐Molecule Organic Solar Cells Enabled by Modulating the Crystallinity of Donors via a Fluorination Strategy

Non-fullerene all-small-molecule organic solar cells (NFSM-OSCs) have shown potential as OSCs, owing to their high purity, easy synthesis and good reproducibility. However, challenges in the modulation of phase separation morphology have limited their development. Herein, two novel small molecular donors, BTEC-1F and BTEC-2F, derived from the small molecule DCAO3TBDTT, are synthesized. Using Y6 as the acceptor, 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 %. The fill factor (FF) of di-fluorinated BTEC-2F-based NFSM-OSC was improved to 72.35 % resulting in a PCE of 13.34 %, which is higher than that of BTEC-1F (61.35 %) and DCAO3TBDTT (60.95 %). To our knowledge, this is the highest PCE for NFSM-OSCs. BTEC-2F had a more compact molecular stacking and a lower crystallinity which enhanced phase separation and carrier transport.