Fluorination Effect for Highly Conjugated Alternating Copolymers Involving Thienylenevinylene-Thiophene-Flanked Benzodithiophene and Benzothiadiazole Subunits in Photovoltaic Application.

Two two-dimensional (2D) donor-acceptor (D-A) type conjugated polymers (CPs), namely, PBDT-TVT-BT and PBDT-TVT-FBT, in which two ((E)-(4,5-didecylthien-2-yl)vinyl)- 5-thien-2-yl (TVT) side chains were introduced into 4,8-position of benzo[1,2-b:4,5-b']dithiophene (BDT) to synthesize the highly conjugated electron-donating building block BDT-TVT, and benzothiadiazole (BT) and/or 5,6-difluoro-BT as electron-accepting unit, were designed to systematically ascertain the impact of fluorination on thermal stability, optoelectronic property, and photovoltaic performance. Both resultant copolymers exhibited the lower bandgap (1.60 ~ 1.69 eV) and deeper highest occupied molecular orbital energy level (E, -5.17 ~ -5.37 eV). It was found that the narrowed absorption, deepened E and weakened aggregation in solid film but had insignificant influence on thermal stability after fluorination in PBDT-TVT-FBT. Accordingly, a PBDT-TVT-FBT-based device yielded 16% increased power conversion efficiency (PCE) from 4.50% to 5.22%, benefited from synergistically elevated V, J, and FF, which was mainly originated from deepened E, increased μ, μ, and more balanced μ/μ ratio, higher exciton dissociation probability and improved microstructural morphology of the photoactive layer as a result of incorporating fluorine into the polymer backbone.