Effect of Electron-Withdrawing Chlorine Substituent on Morphological and Photovoltaic Properties of All Chlorinated D–A-Type Quinoxaline-Based Polymers

The choice of the chlorine (Cl) atom as an electron-withdrawing substituent in conjugated polymers leads to a higher potential in the commercialization of polymer solar cells than its fluorine counterpart because of the versatility and cost-effectiveness of the chlorination process. In addition, the population and location of Cl substituents can significantly influence the photovoltaic characteristics of polymers. In this study, three chlorinated quinoxaline-based polymers were invented to examine the numerical and positioning effects of the Cl atom on their photovoltaic characteristics. The number of Cl substituents in the reference polymer, PBCl-Qx, was adjusted to three: two Cl atoms in the benzodithiophene-type D unit and one Cl atom in the quinoxaline-type A unit. Subsequently, two more Cl atoms were selectively introduced at the 4- and 5-positions of the alkylated thiophene moieties at the 2,3-positions of the quinoxaline moiety in PBCl-Qx to obtain the additional polymers PBCl-Qx4Cl and PBCl-Qx5Cl, respectively. The conventional PBCl-Qx4Cl device exhibited a better power conversion efficiency (PCE) of 12.95% as compared to those of PBCl-Qx (12.44%) and PBCl-Qx5Cl (11.82%) devices. The highest PCE of the device with PBCl-Qx4Cl was ascribed to an enhancement in the open-circuit voltage and fill factor induced by the deeper energy level of the highest occupied molecular orbital and the favorable morphological features in its blended film with Y6.