Delicately Controlled Polymer Orientation for High-Performance Non-Fullerene Solar Cells with Halogen-Free Solvent Processing.

Molecular orientation in polymer solar cells (PSCs) is a critical subject of investigation that promotes the quality of bulk heterojunction morphology and power conversion efficiency (PCE). Herein, the intrinsic polymer orientation transition can be found upon delicate control over the branching point position of the irregular alkoxy side chain in difluoroquinoxaline-thiophene-based conjugated polymers. Three polymers with branching points at the third, fourth, and fifth positions away from the backbone were synthesized and abbreviated as PHT3, PHT4, and PHT5, respectively. Temperature-dependent absorption behavior manifests the polymer aggregation ability in the order of PHT3 < PHT4 < PHT5. Surprisingly, the polymer orientation transition from typical face-on to edge-on emerged between PHT4 and PHT5, as evidenced by X-ray-scattering analysis. The enhanced face-on crystallinity of PHT4 endowed the o-xylene-processed PHT4:IT-4Cl-based devices with the highest PCE of 13.40%. For PHT5 with stronger aggregation, the related o-xylene-processed PSCs still showed a good PCE of 12.66%. Our results demonstrate that a delicate polymer orientation transition could be realized through a precisely controlled strategy of the side chain, yielding green-solvent-processed high-performance PSCs.

Cross-Linkable and Alcohol-Soluble Pyridine-Incorporated Polyfluorene Derivative as a Cathode Interface Layer for High-Efficiency and Stable Organic Solar Cells.

Device performance and commercialization of organic solar cells (OSCs) are strongly influenced by the characteristics of the interface layers. Cross-linked polymer interface layers with solvent-resistant properties are very compatible with large-area solution-processing methods of OSCs and may be beneficial to the environmental stability of OSCs due to the viscoelastic and cross-linked characteristics of the cross-linked polymer. In this work, a novel cross-linkable and alcohol-soluble pyridine-incorporated polyfluorene derivative, denoted as PFOPy, is synthesized and used as a cathode interface layer (CIL) in OSCs. For PFOPy, the pendant epoxy group can be effectively cross linked through cationic polymerization under thermal treatment and the pendant pyridine group can offer good alcohol solubility. Optical absorption tests of PFOPy films before/after washing by chloroform demonstrate the excellent solvent-resistance property for the cross-linked PFOPy film. Compared with the typical ZnO CIL, the cross-linked PFOPy CIL can also substantially reduce ITO's work function and form a better interface contact with the active layer. Utilizing an inverted device structure and a typical active layer of PM6:Y6, ZnO-based OSCs display an optimal power conversion efficiency (PCE) of 15.83% while PFOPy-based OSCs exhibit superior photovoltaic performance with an optimal PCE of 16.20%. Moreover, ZnO-based and PFOPy-based OSCs separately maintain 89% and 90% of the corresponding initial PCE after 12 h of illumination, indicating similarly excellent photostability. More importantly, after 26 complete thermal cycles, ZnO-based OSCs only maintain 81% of the initial PCE while PFOPy-based OSCs retain 92% of the initial PCE and exhibit obviously better thermal cycling stability, indicating that the cross-linked PFOPy CIL should offer stronger interface robustness against thermal cycling stress due to the viscoelastic and cross-linked characteristics of PFOPy. The impressive results indicate that the cross-linked PFOPy CIL would be a very promising CIL in OSCs.