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We compared an indacenodithiophene(IDT)-based fused-ring electron acceptor IDIC1 with its counterpart IHIC1 in which the central benzene unit is replaced by a naphthalene unit, and investigated the effects of the benzene/naphthalene core on the optical and electronic properties as well as on the performance of organic solar cells (OSCs). Compared with benzene-cored IDIC1, naphthalene-cored IHIC1 shows a larger π-conjugation with stronger intermolecular π–π stacking. Relative to benzene-cored IDIC1, naphthalene-cored IHIC1 shows a higher lowest unoccupied molecular orbital energy level (IHIC1: −3.75 eV, IDIC1: −3.81 eV) and a higher electron mobility (IHIC1: 3.0 × 10 −4 cm 2 V −1 s −1 , IDIC1: 1.5 × 10 −4 cm 2 V −1 s −1 ). When paired with the polymer donor FTAZ that has matched energy levels and a complementary absorption spectrum, IHIC1-based OSCs show higher values of open-circuit voltage, short-circuit current density, fill factor and power conversion efficiency relative to those of the IDIC1-based control devices. These results demonstrate that extending benzene in IDT to naphthalene is a promising approach to upshift energy levels, enhance electron mobility, and finally achieve higher efficiency in nonfullerene acceptor-based OSCs. 

Donor polymer fluorination has proven to be an effective method to improve the power conversion efficiency of fullerene-based polymer solar cells (PSCs). However, this fluorine effect has not been well-studied in systems containing new, non-fullerene acceptors (NFAs). Here, we investigate the impact of donor polymer fluorination in NFA-based solar cells by fabricating devices with either a fluorinated conjugated polymer (FTAZ) or its non-fluorinated counterpart (HTAZ) as the donor polymer and a small molecule NFA (ITIC) as the acceptor. We found that, similar to fullerene-based devices, fluorination leads to an increased open circuit voltage ( V oc ) from the lowered HOMO level and improved fill factor (FF) from the higher charge carrier mobility. More importantly, donor polymer fluorination in this NFA-based system also led to a large increase in short circuit current ( J sc ), which stems from the improved charge transport and extraction in the fluorinated device. This study demonstrates that fluorination is also advantageous in NFA-based PSCs and may improve performance to a higher extent than in fullerene-based PSCs. In the context of other recent reports on demonstrating higher photovoltaic device efficiencies with fluorinated materials, fluorination appears to be a valuable strategy in the design and synthesis of future donors and acceptors for PSCs. 

Abstract Incorporating narrow‐bandgap near‐infrared absorbers as the third component in a donor/acceptor binary blend is a new strategy to improve the power conversion efficiency (PCE) of organic photovoltaics (OPV). However, there are two main restrictions: potential charge recombination in the narrow‐gap material and miscompatibility between each component. The optimized design is to employ a third component (structurally similar to the donor or acceptor) with a lowest unoccupied molecular orbital (LUMO) energy level similar to the acceptor and a highest occupied molecular orbital (HOMO) energy level similar to the donor. In this design, enhanced absorption of the active layer and enhanced charge transfer can be realized without breaking the optimized morphology of the active layer. Herein, in order to realize this design, two new narrow‐bandgap nonfullerene acceptors with suitable energy levels and chemical structures are designed, synthesized, and employed as the third component in the donor/acceptor binary blend, which boosts the PCE of OPV to 11.6%.