Regio-regular alternating diketopyrrolopyrrole-based D₁-A-D₂-A terpolymers for the enhanced performance of polymer solar cells

We designed and synthesized regio-regular alternating diketopyrrolopyrrole (DPP)-based D₁-A-D₂-A terpolymers (PDPPF2T2DPP-T2, PDPPF2T2DPP-TVT, and PDPPF2T2DPP-DTT) using a primary donor (D₁) [3,3′-difluoro-2,2′-bithiophene (F2T2)] and a secondary donor (D₂) [2,2′-bithiophene (T2), (E)-1,2-di(thiophen-2-yl)ethene (TVT), or dithieno[3,2-b:2′,3′-d]thiophene (DTT)]. A PDPP2DT-F2T2 D-A polymer was synthesized as well to compare optical, electronic, and photovoltaic properties. The absorption peaks of the terpolymers (PDPPF2T2DPP-T2, PDPPF2T2DPP-TVT, and PDPPF2T2DPP-DTT) were longer (λ_max = 801-810 nm) than the peak of the PDPP2DT-F2T2 polymer (λ_max = 799 nm), which is associated with the high-lying HOMO levels of the terpolymers (-5.08 to -5.13 eV) compared with the level of the PDPP2DT-F2T2 polymer (-5.38 eV). The photovoltaic properties of these DPP-based polymers were investigated under simulated AM 1.5G sunlight (100 mW cm^-2) with a conventional structure (ITO/PEDOT:PSS/polymer:PC₇₁BM/Al). The open-circuit voltages (V_oc) of photovoltaic devices containing the terpolymers were slightly lower (0.68-0.70 V) than the V_oc of the device containing the PDPP2DT-F2T2 polymer (0.79 V). The short-circuit current (J_sc) of the PDPPF2T2DPP-DTT device was significantly improved (14.14 mA cm^-2) compared with that of the PDPP2DT-F2T2 device (8.29 mA cm^-2). As a result, the power conversion efficiency (PCE) of the PDPPF2T2DPP-DTT device (6.35%) was increased by 33% compared with that of the simple D-A-type PDPP2DT-F2T2 device (4.78%). The highest J_sc and PCE values (the PDPPF2T2DPP-DTT device) were attributed to an optimal nanoscopically mixed morphology and strong interchain packing with a high face-on orientation in the blend film state. The study demonstrated that our strategy of using multiple donors in a regio-regular alternating fashion could fine-tune the optical, electronic, and morphological properties of D-A-type polymers, enhancing the performance of polymer solar cells.