Fine Tuning of Open-Circuit Voltage by Chlorination in Thieno[3,4‑<i>b</i>]thiophene–Benzodithiophene Terpolymers toward Enhanced Solar Energy Conversion

A new family of thieno­[3,4-<i>b</i>]­thiophene–benzodithiophene terpolymers (PBTClx) have been designed and synthesized, in which the chlorine/fluorine content has been adjusted and optimized. As the content of chlorine is increased in polymers, the twist angle between the donor and acceptor is increased, which leads to a diminishment in the planarity and conjugation. As a result, the UV–vis absorption is continuous blue-shifted, and the band gap increases from 1.57 to 2.04 eV when the chlorinated moieties increased from 0 to 100%. The highest occupied molecular orbital (HOMO) levels of those polymers are decreased by increasing the content of chlorinated moiety, which opens a window to constantly modify the <i>V</i><sub>oc</sub> values and eventually meets a balance point for optimized solar energy conversion. The highest power conversion efficiency of 8.31% is obtained by using <b>PBTCl25</b> as the donor and PC<sub>71</sub>BM as the acceptor in polymer solar cells (PSCs), in which the <i>V</i><sub>oc</sub> increased from 0.79 to 0.82 V after 25% chlorinated monomer involved in copolymerization. Herein, the chlorine replacement could be a good method to further pump the solar conversion by increasing the open circuit voltage without reducing other factors of the polymer solar cells.