Phenanthroline-carbolong interface suppress chemical interactions with active layer enabling long-time stable organic solar cells.

To restrain the chemical reaction at cathode interface of organic solar cells, two cathode interfacial materials are synthesized by connecting phenanthroline with carbolong unit. Consequently, the D18:L8-BO based organic solar cell with double-phenanthroline-carbolong achieve the highest efficiency of 18.2%. Double-phenanthroline-carbolong with larger steric hindrance and stronger electron-withdrawing property confirms to suppress the interfacial reaction with norfullerene acceptor, resulting the most stable device. Double-phenanthroline-carbolong based device can sustain 80% of its initial efficiency for 2170 h in dark N2 atmosphere, 96 h under 85 oC and keep 68% initial efficiency after been illuminated for 2200 h, which are significantly better than bathocuproin based devices. Moreover, superb interfacial stability of double-phenanthroline-carbolong cathode interface enables thermal posttreatment of organic sub-cell in perovskite/organic tandem solar cells and obtained a remarkable efficiency of 21.7% with excellent thermal stability, which indicates the potentially wide application of phenanthroline-carbolong materials for stable and efficient solar device fabrications.

Chlorination: An Effective Strategy for High-Performance 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.

Electron-Deficient and Quinoid Central Unit Engineering for Unfused Ring-Based A1 -D-A2 -D-A1 -Type Acceptor Enables High Performance Nonfullerene Polymer Solar Cells with High Voc and PCE Simultaneously.

Here, a pair of A1 -D-A2 -D-A1 unfused ring core-based nonfullerene small molecule acceptors (NF-SMAs), BO2FIDT-4Cl and BT2FIDT-4Cl is synthesized, which possess the same terminals (A1 ) and indacenodithiophene unit (D), coupling with different fluorinated electron-deficient central unit (difluorobenzoxadiazole or difluorobenzothiadiazole) (A2 ). BT2FIDT-4Cl exhibits a slightly smaller optical bandgap of 1.56 eV, upshifted highest occupied molecular orbital energy levels, much higher electron mobility, and slightly enhanced molecular packing order in neat thin films than that of BO2FIDT-4Cl. The polymer solar cells (PSCs) based on BT2FIDT-4Cl:PM7 yield the best power conversion efficiency (PCE) of 12.5% with a Voc of 0.97 V, which is higher than that of BO2FIDT-4Cl-based devices (PCE of 10.4%). The results demonstrate that the subtle modification of A2 unit would result in lower trap-assisted recombination, more favorable morphology features, and more balanced electron and hole mobility in the PM7:BT2FIDT-4Cl blend films. It is worth mentioning that the PCE of 12.5% is the highest value in nonfused ring NF-SMA-based binary PSCs with high Voc over 0.90 V. These results suggest that appropriate modulation of the quinoid electron-deficient central unit is an effective approach to construct highly efficient unfused ring NF-SMAs to boost PCE and Voc simultaneously.

Unraveling the Microstructure-Related Device Stability for Polymer Solar Cells Based on Nonfullerene Small-Molecular Acceptors.

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.

3D Interpenetrating Network for High-Performance Nonfullerene Acceptors via Asymmetric Chlorine Substitution.

Two chlorine-substituted isomers, ITIC-2Cl-ß and a-ITIC-2Cl, were synthesized for potential use as nonfullerene acceptors. The two molecules differ in the position of chlorine atoms, leading to symmetric (ITIC-2Cl-ß) and asymmetric (a-ITIC-2Cl) molecular configuration. In single crystals, the two molecules exhibit a completely different arrangement and stacking as derived from X-ray diffraction analysis. Whereas ITIC-2Cl-ß has a linear packing structure, a-ITIC-2Cl forms a 3D interpenetrating network structure with shorter π-π distances and better molecular planarity. Therefore, a high power conversion efficiency of >12% is obtained by a-ITIC-2Cl-based devices. It is ∼10% higher than that of ITIC-2Cl-ß-based devices due to the chlorine substituent effect. Thus the fine-tuning of the Cl-substituted position seems to be a promising strategy to construct a 3D interpenetrating charge transportation network and achieve higher performance organic solar cells (OSCs).

Isomer-free: Precise Positioning of Chlorine-Induced Interpenetrating Charge Transfer for Elevated Solar Conversion.

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.

Carrier Dynamics and Morphology Regulated by 1,8-Diiodooctane in Chlorinated Nonfullerene Polymer Solar Cells.

Very small amounts of 1,8-diiodooctane (DIO) are very effective at optimizing the performance of polymer solar cells (PSCs). To date, the underlying influences are not yet fully understood, especially in nonfullerene PSCs. Herein, the influence of DIO on carrier dynamics and morphology in the PBDBT2Cl:IT4F system was investigated in detail. We combined the characterization of the transient dynamics with the morphology characterization of PSC devices to explore the origin of enhanced performance. Compared to the cast device, the champion device with 0.5% DIO revealed the maximum of current density ( Jsc) and fill factor (FF). The optimum DIO content helps to enhance carrier transport and optimize morphology, while excess DIO produces adverse effects due to the induced intense aggregation and dilated size in blend films. The results provide some hints of improved device performance upon using DIO as an additive in nonfullerene PSCs.

Chlorine Atom-Induced Molecular Interlocked Network in a Non-Fullerene Acceptor.

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 1,1-dicyanomethylene-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.