Non-fullerene Acceptors (NFAs) have gathered a great deal of interest for use inorganic photovoltaics (OPVs) due to recent breakthroughs in their power conversion efficiency and other advantages they offer over their Fullerene-based counterparts.
In this work, a new promising non-fullerene polymer acceptor, PF5-Y5, have been studied using density functional theory and time-dependent density functional theory; and the effects that oligomer length, geometry relaxation and exchange-correlation interaction has on the exciton binding energies (the difference between optical and fundamental energy gaps) have been investigated.
Both the fundamental and optical gaps are significantly affected by the choice of functional (i.e., the description of the exchange-correlation interaction). However, it does not appear to significantly impact obtained exciton binding energies as the effects of the fundamental and optical gaps cancel each other out.
Both the fundamental and optical energy gap are shown to slightly reduce as a function of the oligomer length (~0.1 - 0.3 𝑒𝑉 reduction for each repeated monomer). As both gaps are reduced by a similar amount per repeated monomer, they counteract each other and the total effect that oligomer length has on the exciton binding energy is very low.
Geometry relaxation and thermal effects showed the largest impact on the fundamental gap and exciton binding energy, with their combined effect resulting in a ~0.5 𝑒𝑉 reduction in binding energy.