An Effective Strategy to Design a Large Bandgap Conjugated Polymer by Tuning the Molecular Backbone Curvature

Abstract

With the significant progress of low bandgap non-fullerene acceptors, the development of wide bandgap (WBG) donors possessing ideal complementary absorption is of crucial importance to further enhance the photovoltaic performance of organic solar cells. An ideal strategy to design WBG donors is to down-shift the highest occupied molecular orbital (HOMO) and up-shift the lowest unoccupied molecular orbital (LUMO). A properly low-lying HOMO of the donor is favorable to obtaining a high open-circuit voltage, and a properly high-lying LUMO of the donor is conductive to efficient exciton dissociation. This work provides a new strategy to enlarge the bandgap of a polymer with simultaneously decreased HOMO and increased LUMO by increasing the polymer backbone curvature. The polymer PIDT-fDTBT with a large molecular backbone curvature shows a decreased HOMO of -5.38 eV and a prominently increased LUMO of -3.35 eV relative to the linear polymer PIDT-DTBT (E_HOMO = -5.30 eV, E_LUMO = -3.55 eV). The optical bandgap of PIDT-fDTBT is obviously broadened from 1.75 to 2.03 eV. This work demonstrates that increasing the polymer backbone curvature can effectively broaden the bandgap by simultaneously decreasing HOMO and increasing LUMO, which may guide the design of WBG conjugated materials.

Keywords: energy levels; optoelectronic properties; organic solar cells; polymer backbone curvature; wide bandgap materials.