The bulk-heterojunction blend of an electron donor and an electron acceptor material is the key component in a solution-processed organic photovoltaic device. In the past decades, a p-type conjugated polymer and an n-type fullerene derivative have been the most commonly used electron donor and electron acceptor, respectively. While most advances of the device performance come from the design of new polymer donors, fullerene derivatives have almost been exclusively used as electron acceptors in organic photovoltaics. Recently, nonfullerene acceptor materials, particularly small molecules and oligomers, have emerged as a promising alternative to replace fullerene derivatives. Compared to fullerenes, these new acceptors are generally synthesized from diversified, low-cost routes based on building block materials with extraordinary chemical, thermal, and photostability. The facile functionalization of these molecules affords excellent tunability to their optoelectronic and electrochemical properties. Within the past five years, there have been over 100 nonfullerene acceptor molecules synthesized, and the power conversion efficiency of nonfullerene organic solar cells has increased dramatically, from ∼2% in 2012 to >13% in 2017. This review summarizes this progress, aiming to describe the molecular design strategy, to provide insight into the structure-property relationship, and to highlight the challenges the field is facing, with emphasis placed on most recent nonfullerene acceptors that demonstrated top-of-the-line photovoltaic performances. We also provide perspectives from a device point of view, wherein topics including ternary blend device, multijunction device, device stability, active layer morphology, and device physics are discussed.

Figure 1. a) The synthetic routes of IC-Br(in) and IC-Br(out). b) Chemical structures of PY-IT, PY-OT and PY-IOT.

We report a novel small molecule acceptor (SMA) named FTTB-PDI4 obtained via ring-fusion between the thiophene and perylene diimide (PDI) units of a PDI-tetramer with a tetrathienylbezene (TTB) core. A small voltage loss of 0.53 V and a high power conversion efficiency of 10.58% were achieved, which is the highest value reported for PDI-based devices to date. By comparing the fused and nonfused SMAs, we show that the ring-fusion introduces several beneficial effects on the properties and performances of the acceptor material, including more favorable energy levels, enhanced light absorption and stronger intermolecular packing. Interestingly, morphology data reveal that the fused molecule yields higher domain purity and thus can better maintain its molecular packing and electron mobility in the blend. Theoretical calculations also demonstrate that FTTB-PDI4 exhibits a "double-decker" geometry with two pairs of mostly parallel PDI units, which is distinctively different from reported PDI-tetramers with highly twisted geometries and can explain the better performance of the material. This work highlights the promising design of PDI-based acceptors by the ring-fusion strategy.