Wide Band‐Gap Polymer Donors Functionalized with Unconventional Carbamate Side Chains for Polymer Solar Cells.

Side‐chain engineering with heteroatoms is not only effective in tuning frontier molecular orbitals, but also possible for forming secondary bonds which can be utilized to planarize the molecular backbone, hence, improving the photon absorption as well as charge‐transport abilities of polymer solar‐cell (PSC) materials. Herein, two types of unconventional side chains, namely carboxylate and carbamate, containing various heteroatoms are introduced to the thiophene bridges in high performance benzodithiophene (BDT) based donor polymers to from the novel polymers PTzTz‐C and PTzTz‐N, respectively. In these polymers, non‐covalent O⋅⋅⋅S and N⋅⋅⋅H interactions induce a high tendency to aggregation. In a ternary‐blend PSC with PTzTz‐N added to the high‐performance D18 : BTP‐eC9 blend, complimentary absorption and improved thin‐film morphology were observed with a top power conversion efficiency of 18.76 %, which is an improvement of almost 5 % over the D18 : BTP‐eC9 binary blends. [ABSTRACT FROM AUTHOR]