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

摘要

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 similar to 1.69 eV) and deeper highest occupied molecular orbital energy level (EHOMO, -5.17 similar to -5.37 eV). It was found that the narrowed absorption, deepened EHOMO 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-OC, J(SC), and FF, which was mainly originated from deepened E-HOMO, increased mu(h), mu(e), and more balanced mu(h)/mu(e) ratio, higher exciton dissociation probability and improved microstructural morphology of the photoactive layer as a result of incorporating fluorine into the polymer backbone.