As the power conversion efficiency (PCE) of organic solar cells (OSCs)has surpassed the 17% baseline, the long-term stability of highly efficient OSCs is essential for the practical application of this photovoltaic technology. Here, the photostability and possible degradation mechanisms of three state-of-the-art polymer donors with a commonly used nonfullerene acceptor (NFA), IT-4F, are investigated. The active-layer materials show excellent intrinsic photostability. The initial morphology, in particular the mixed region, causes degradation predominantly in the fill factor (FF) under illumination. Electron traps are formed due to the reorganization of polymers and diffusion-limited aggregation of NFAs to assemble small isolated acceptor domains under illumination. These electron traps lead to losses mainly in FF, which is in contradistinction to the degradation mechanisms observed for fullerene-based OSCs. Control of the composition of NFAs close to the thermodynamic equilibrium limit while keeping adequate electron percolation and improving the initial polymer and NFA ordering are of the essence to stabilize the FF in NFA-based solar cells, which may be the key tactics to develop next-generation OSCs with high efficiency as well as excellent stability.

We reported a chlorinated polymer donor PBT4T-Cl that showed a high PCE of 11.18%. The results demonstrated chlorination of the thiophene moiety could finetune the HOMO level of the corresponding polymer as well as the carrier mobility and morphologies of the blend film, eventually improving its photovoltaic properties as a donor without thermal annealing.

The differences between the introduction of chlorine and fluorine atoms to small-molecule acceptors were deeply investigated. From the single-crystal structures of three molecules, the Cl-substitution intervention into the molecular configuration and packing mainly lies in three aspects as follows: single molecule configuration, one direction of the intermolecular arrangement, and three-dimensional (3D) molecular packing. First, the introduction of the chlorine atom in IDIC-4Cl leads to a more planar molecular configuration than IDIC-4H and IDIC-4F because of the formation of a molecular interlocked network induced by the strong Cl•••S intermolecular interactions. Second, IDIC-4Cl shows the closest π−π stacking distance and the smallest dihedral angle (0°) between adjacent molecules to form ideal J-aggregation, which should be beneficial for charge transportation between different connected molecules in this direction. Finally, the interlocked interactions between Cl and S atoms lead to a highly ordered 3D molecular packing, in which the end groups will form an ideal overlapped packing among different molecules, whereas the other two analogues with H or F show less ordered packing of their 1,1dicyanomethylene-3-indanone ending groups. Organic solar cells based on IDIC-4Cl show the highest power conversion efficiency (PCE) of 9.24%, whereas the PCEs of IDIC-4H-and IDIC-4F-based devices are 4.57 and 7.10%, respectively.

Summary The influence caused by the position of the chlorine atom on end groups of two non-fullerene acceptors ( ITIC-2Cl-δ and ITIC-2Cl-γ ) was intensely investigated. The single-crystal structures show that ITIC-2Cl-γ has a better molecular planarity and closer π-π interaction distance. More importantly, a 3D rectangle-like interpenetrating network is formed in ITIC-2Cl-γ and is beneficial to rapid charge transfer along multiple directions, whereas only a linear stacked structure could be observed in ITIC-2Cl-δ . The two acceptor-based solar cells show power conversion efficiencies (PCEs) over 11%, higher than that of the ITIC-2Cl- m -based device (10.85%). An excellent PCE of 13.03% is obtained by the ITIC-2Cl-γ -based device. In addition, the ITIC-2Cl-γ -based device also shows the best device stability. This study indicates that chlorine positioning has a great impact on the acceptors; more importantly, the 3D network structure may be a promising strategy for non-fullerene acceptors to improve the PCE and stability of organic solar cells.

This work summarizes recent developments in polymer solar cells (PSCs) prepared by a chlorination strategy. The intrinsic property of chlorine atoms, the progress of chlorinated polymers and small molecules, and the synergistic effect of chlorination with other methods to elevate solar conversions are discussed. Halogenation of donor–acceptor (D–A) materials is an effective method to improve the performance of PSCs, which mainly affects the push–pull of electrons between donor and acceptor units due to their strong electron‐withdrawing capabilities. Although chlorine is less electronegative than fluorine, it can form very strong noncovalent interactions, such as Cl···S and Cl··· π interactions, because its empty 3d orbits can help to accept the electron pairs or π electrons. This synergistic effect of electronegativity together with the empty 3d orbits of chlorine atoms leads to increased intramolecular and intermolecular interactions and a much stronger capability to down‐shift the molecular energy levels. This work is intended to support a better understanding of the chlorination strategy to modify the material properties, and thus improve the performance of solar devices. Eventually, it will provide the research community with a clearer pathway to choose proper substitution methods according to different situations for high and stable solar energy conversion.