In organic photovoltaics, morphological control of donor and acceptor domains on the nanoscale is key for efficient exciton diffusion and dissociation, carrier transport, and suppression of recombination losses. To realise this, here, we demonstrated a double-fibril network based on ternary donor:acceptor morphology with multi-length scales constructed by combining ancillary conjugated polymer crystallizers and non-fullerene acceptor filament assembly. Using this approach, we achieved an average power conversion efficiency of 19.3% (certified 19.2%). The success lies in the good match between the photoelectric parameters and the morphological characteristic lengths, which utilizes the excitons and free charges efficiently. This strategy leads to enhanced exciton diffusion length (hence exciton dissociation yield) and reduced recombination rate, hence minimizing photon-to-electron losses in the ternary devices as compared to their binary counterparts. The double-fibril network morphology strategy minimizes losses and maximizes the power output, offering the possibility towards 20% power conversion efficiencies in single-junction organic photovoltaics. MainOrganic semiconductors offer the advantage of high optical absorption and tunable energy levels, enabling thin-film solar cells with high light-to-electron conversion efficiencies over a wide range of wavelengths [1][2][3][4] . Desipte recent progresses, the performance of organic solar cells (OSCs) is still limited by non-ideal exciton and charge transport, which depend not only on the electronic structure of organic semiconductors but also on the nanostructure that is formed by material crystallization and phase separation in a bulk heterojunction (BHJ) setting [5][6][7][8] . A suitable sized phase-separated morphology that balances crystalline region and mixing domain on the nanoscale is therefore needed to further push the power conversion efficiency (PCE) of OSCs, however it is a

The performance of solar cells based on molecular electronic materials is limited by relatively high nonradiative voltage losses. The primary pathway for nonradiative recombination in organic donoracceptor heterojunction devices is believed to be the decay of a charge-transfer (CT) excited state to the ground state via energy transfer to vibrational modes. Recently, nonradiative voltage losses have been related to properties of the charge-transfer state such as the Franck-Condon factor describing the overlap of the CT and ground-state vibrational states and, therefore, to the energy of the CT state. However, experimental data do not always follow the trends suggested by the simple model. Here, we extend this recombination model to include other factors that influence the nonradiative decay-rate constant, and therefore the open-circuit voltage, but have not yet been explored in detail. We use the extended model to understand the observed behavior of series of small molecules:fullerene blend devices, where open-circuit voltage appears insensitive to nonradiative loss. The trend could be explained only in terms of a microstructure-dependent CT-state oscillator strength, showing that parameters other than CT-state energy can control nonradiative recombination. We present design rules for improving open-circuit voltage via the control of material parameters and propose a realistic limit to the power-conversion efficiency of organic solar cells.

Organic solar cells (OSCs) based on nonfullerene acceptors (NFAs) have made significant breakthrough in their device performance, now achieving a power conversion efficiency of ≈18% for single junction devices, driven by the rapid development in their molecular design and device engineering in recent years. However, achieving long‐term stability remains a major challenge to overcome for their commercialization, due in large part to the current lack of understanding of their degradation mechanisms as well as the design rules for enhancing their stability. In this review, the recent progress in understanding the degradation mechanisms and enhancing the stability of high performance NFA‐based OSCs is a specific focus. First, an overview of the recent advances in the molecular design and device engineering of several classes of high performance NFA‐based OSCs for various targeted applications is provided, before presenting a critical review of the different degradation mechanisms identified through photochemical‐, photo‐, and morphological degradation pathways. Potential strategies to address these degradation mechanisms for further stability enhancement, from molecular design, interfacial engineering, and morphology control perspectives, are also discussed. Finally, an outlook is given highlighting the remaining key challenges toward achieving the long‐term stability of NFA‐OSCs.

We report the synthesis of a family of multifluorine substituted oligomers and the corresponding polymer that have the same backbones but different conjugation lengths and amounts of fluorine atoms on the backbone. The physical properties and photovoltaic performances of these materials were systematically investigated using optical absorption, charge mobility, atomic force microscopy, transmission electron microscopy, grazing incidence X-ray diffraction, resonant soft X-ray scattering methods, and photovoltaic devices. The power conversion efficiencies (PCEs) based on oligomers were much higher than that in the polymer. Moreover, the devices based on BIT6F and BIT10F, which have an axisymmetric electron-deficient difluorobenzothiadiazole as the central unit, gave slightly higher PCEs than those with centrosymmetric electron-rich indacenodithiophene (IDT) as the central unit (BIT4F or BIT8F). Using proper solvent vapor annealing (SVA), particularly using thermal annealing (TA) followed by SVA, the device performance could be significantly improved. Notably, the best PCE of 9.1% with a very high FF of 0.76 was achieved using the medium-sized oligomer BIT6F with the optimized film morphology. This efficiency is the highest value reported for organic solar cells from small-molecules without rhodanine terminal group. More excitingly, devices from the shortest oligomer BIT4F showed an impressively high FF of 0.77 (the highest FF value reported for solution-processed small-molecule organic solar cells). These results indicate that photovoltaic performances of oligomers can be modulated through successive change in chain-length and fluorine atoms, alternating spatial symmetric core, and combined post-treatments.