A series of polythiophenes (PTs) functionalized with bulky conjugated side chains comprising tert-butylsubstituted carbazole (tCz) as an electron donor pendant and bisbenzothiazolylvinyl (DBT) as anelectron acceptor pendant were synthesized via Stille copolymerization for polymer solar cell (PSC)applications. We use the descriptors PTtCz, PT(tCz)0.9(DBT)0.1, PT(tCz)0.64(DBT)0.36, PT(tCz)0.45(DBT)0.55,and PTDBT to identify each of these conjugated polymers, with the names denoting the compositionsof the bulky pendants. The tunable energy levels of the PTs were accomplished by incorporating bothtCz as a donor pendant and DBT as an acceptor pendant, while retaining the low-lying HOMO levels( 5.26 to 5.39 eV). Furthermore, lower bandgaps were observed for the DBT-derived PTs because ofstronger donor–p–acceptor characteristics and more efficient intramolecular charge transfer.Conventional PSCs were fabricated by spin-coating the blend of each PT and the fullerene derivative(PC71BM). The conventional PSC devices exhibited high open circuit voltages (Voc) of around 0.79–0.91 V. The power conversion efficiency (PCE) of the PSCs based on PTtCz : PC71BM (w/w ¼ 1 : 2.5)reached 2.48% with a Voc of 0.91 V, short circuit current (Jsc) of 6.58 (mA cm 2) and fill factor (FF) of41% under the illumination of AM1.5, 100 mW cm 2. Furthermore, a PTtCz/PC71BM-based inverted PSCwith ZnOx and MoO3 as an electron extraction layer and a hole extraction layer respectively was capableof retaining ca. 80% of its original efficiency after storage under ambient conditions (withoutencapsulation) for 1032 h, according to the ISOS-D-1 shelf protocol. The highly durable inverted PSCaccompanied by a large Voc value was achieved for the PT-type polymers
