Thiophene-Fused Perylenediimide-Based Polymer Acceptors for High-Performance All-Polymer Solar Cells

Over the past years, perylenediimide (PDI)-based polymers have emerged as one of the widely studied polymer acceptors applicable to all-polymer solar cells (PSCs) due to their outstanding photovoltaic properties. Covalently fused PDI units, such as naphthodiperylenetetraimide (NDP), are proven beneficial to increasing the regularity of polymer backbones and enhancing the molecular packing in blend films, thus optimizing the active-layer morphology and improving the device performance. However, most investigated PDI polymers commonly demonstrated low open-circuit voltage (V-oc) in solar cells due to their low-lying lowest unoccupied molecular orbital (LUMO), which greatly limited the power-conversion efficiencies (PCEs) of their devices. Herein, we design and synthesize two new polymer acceptors (PTP-TT and PTP-Th) using thiophene-fused dimeric PDI (i.e., PTP) as the key building block. Both polymers exhibit much elevated LUMO levels at ca. -3.8 eV and achieve higher V-oc in devices compared with NDP-derived polymers. In particular, PTP-TT exhibits stronger light-absorption ability than PTP-Th and a presumably more planar backbone conformation, which are favorable for molecular packing and charge carrier transport in the active layer. Using PTB7-Th as the donor, PTP-TT-based devices achieve the best PCE of 7.04%, with a V-oc of 0.86 V, a short-circuit current density of 14.96 mA/cm(2), and a fill factor of 54%. The current results demonstrate that fusing PDIs with a proper electron-rich moiety can synergistically elevate the LUMO level and optimize the backbone regularity of polymer acceptors to obtain desirable efficiencies of PSCs.