Solution‐Processed Organic Solar Cells with High Open‐Circuit Voltage of 1.3 V and Low Non‐Radiative Voltage Loss of 0.16 V

<jats:title>Abstract</jats:title><jats:p>Compared with inorganic or perovskite solar cells, the relatively large non‐radiative recombination voltage losses (Δ<jats:italic>V</jats:italic><jats:sub>non‐rad</jats:sub>) in organic solar cells (OSCs) limit the improvement of the open‐circuit voltage (<jats:italic>V</jats:italic><jats:sub>oc</jats:sub>). Herein, OSCs are fabricated by adopting two pairs of D–π–A polymers (PBT1‐C/PBT1‐C‐2Cl and PBDB‐T/PBDB‐T‐2Cl) as electron donors and a wide‐bandgap molecule BTA3 as the electron acceptor. In these blends, a charge‐transfer state energy (<jats:italic>E</jats:italic><jats:sub>CT</jats:sub>) as high as 1.70–1.76 eV is achieved, leading to small energetic differences between the singlet excited states and charge‐transfer states (Δ<jats:italic>E</jats:italic><jats:sub>CT</jats:sub> ≈ 0.1 eV). In addition, after introducing chlorine atoms into the π‐bridge or the side chain of benzodithiophene (BDT) unit, electroluminescence external quantum efficiencies as high as 1.9 × 10<jats:sup>−3</jats:sup> and 1.0 × 10<jats:sup>−3</jats:sup> are realized in OSCs based on PBTI‐C‐2Cl and PBDB‐T‐2Cl, respectively. Their corresponding Δ<jats:italic>V</jats:italic><jats:sub>non‐rad</jats:sub> are 0.16 and 0.17 V, which are lower than those of OSCs based on the analog polymers without a chlorine atom (0.21 and 0.24 V for PBT1‐C and PBDB‐T, respectively), resulting in high <jats:italic>V</jats:italic><jats:sub>oc</jats:sub> of 1.3 V. The Δ<jats:italic>V</jats:italic><jats:sub>non‐rad</jats:sub> of 0.16 V and <jats:italic>V</jats:italic><jats:sub>oc</jats:sub> of 1.3 V achieved in PBT1‐C‐2Cl:BTA3 OSCs are thought to represent the best values for solution‐processed OSCs reported in the literature so far.</jats:p>