Tuning the electronic and optical properties of NDT-based conjugated polymers by adopting fused heterocycles as acceptor units: a theoretical study.

Donor-acceptor conjugated polymers have been successfully applied in bulk heterojunction solar cell devices. Tuning their donor and acceptor units allows the design of new polymers with desired electronic and optical properties. Here, to screen new candidate polymers based on a newly synthesized donor unit, dithieo[2,3-d:2',3'-d']naphtho[1,2-b:3,4-b']dithiophene (NDT), a series of model polymers with different acceptor units were designed and denoted NDT-A0 to NDT-A12, and the structures and optical properties of those polymers were investigated using DFT and TDDFT calculations. The results of the calculations revealed that the electronic and optical properties of these polymers depend on the acceptor unit present; specifically, their HOMO energies ranged from -4.89 to -5.38 eV, their HOMO-LUMO gaps ranged from 1.30 to 2.80 eV, and their wavelengths of maximum absorption ranged from 538 to 1212 nm. The absorption spectra of NDT-A1 to NDT-A6, NDT-A8, NDT-A9, and NDT-A12 occur within the visible region (<900 nm), indicating that these polymers are potential candidates for use in solar cells. On the other hand, the absorption spectra of NDT-A7, NDT-A10, and NDT-A11 extend much further into the near-infrared region, implying that they absorb near-infrared light. These polymers could meet the requirements of donor units for use in tandem and ternary solar cells. Graphical abstract Theoretical calculations by TD-DFT reveal that the optical properties of NDT-based conjugated polymers can be well tuned by adopting different acceptor units, and these ploymers are potential donor materials for tandem and ternary solar cells.