Side-Chain Influence of Wide-Bandgap Copolymers Based on Naphtho[1,2-b:5,6-b]bispyrazine and Benzo[1,2-b:4,5-b']dithiophene for Efficient Photovoltaic Applications.

In this work, we reported new types of wide-bandgap copolymers, PBDTA-NPz, PBDTT-NPz, PBDTF-NPz, and PBDTP-NPz, on the basis of the naphtho[1,2-b:5,6-b]bispyrazine (NPz) acceptor building block for efficient photovoltaic applications. The influencing factors of the introduced side chains, including alkoxyl, alkylthienyl, alkylfuryl, and alkoxylphenyl, were investigated in detail. These copolymers possessed wide bandgaps ranging from 1.79 to 1.88 eV with different nonconjugated or conjugated side chains. They also possessed deep highest-occupied molecular orbital levels of less than -5.25 eV, which allowed the achievement of high Voc's from their polymer solar cells (PSCs). The X-ray diffraction results indicated their excellent crystallinity and molecular stacking features, especially for PBDTF-NPz containing alkylfuryl side chains. Their photovoltaic performances were measured using bulk-heterojunction single-junction PSCs with a configuration of ITO/PEDOT:PSS/copolymer:PC71BM/Ca/Al under the same processing conditions. Different side chains of NPz-based copolymers induced largely different device performances. Without the additive, 1,8-diiodooctane (DIO), the primary PBDTA-NPz, PBDTT-NPz, PBDTF-NPz, and PBDTP-NPz devices showed power conversion efficiencies (PCEs) of 4.53, 6.09, 7.06, and 3.49%, respectively. On adding 3 vol % DIO, the device performances were elevated to a higher level. The PBDTF-NPz devices exhibited the highest PCE of 8.63%, which resulted in improved Voc, Jsc, and FF values caused by their inherent properties. Our results indicated that NPz is a potential acceptor unit to construct high-powered wide-bandgap copolymers for efficient PSCs in the future.