Among the emerging photovoltaic technologies, rigid perovskite solar cells (PSCs) have made tremendous development owing to their exceptional power conversion efficiency (PCE) of up to 25.7%. However, the record PCE of flexible PSCs (≈22.4%) still lags far behind their rigid counterparts and their mechanical stabilities are also not satisfactory. Herein, through modifying the interface between perovskite and hole transport layer via pentylammonium acetate (PenAAc) molecule a highly efficient and stable flexible inverted PSC is reported. Through synthetic manipulation of anion and cation, it is shown that the PenA+ and Ac− have strong chemical binding with both acceptor and donor defects of surface‐terminating ends on perovskite films. The PenAAc‐modified flexible PSCs achieve a record PCE of 23.68% (0.08 cm2, certified: 23.35%) with a high open‐circuit voltage (VOC) of 1.17 V. Large‐area devices (1.0 cm2) also realized an exceptional PCE of 21.52%. Moreover, the fabricated devices show excellent stability under mechanical bending, with PCE remaining above 91% of the original PCE even after 5000 bends.

All‐polymer solar cells (all‐PSCs) have achieved impressive progress in photovoltaic performance and stabilities recently. However, their power conversion efficiencies (PCEs) still trail that of small‐molecular acceptor‐based organic solar cells (>19%) mainly because of the inferior fill factor (FF). Herein, a combined homo hydrocarbon solvent and sequential deposition (SD) strategy is presented to boost the FF of rigid all‐PSCs to 77.7% and achieve a superior PCE of 17.7% with excellent stability, which is among the highest efficiencies reported for all‐PSCs thus far. Meanwhile, a remarkable PCE of 14.5% is realized for flexible all‐PSCs with outstanding mechanical stability. The blend film morphologies measurements suggest that the SD method enables the formation of an ideal pseudo‐bilayer film with bicontinuous interdigitated structure and ordered polymer packing. The numerical simulation result indicates that the FF enhancement mainly results from the efficient exciton diffusion dynamics, increased carrier mobilities, and more balanced electron/hole mobility ratio induced by the developed SD method. This is also confirmed by the FF loss analysis, which manifests that the reduced series resistance and increased shunt resistance are the main reasons for the reduction of FF loss. This work provides a promising strategy to fabricate highly efficient and stable all‐PSCs to promote their future development and practical manufacturing.

realized, PVSCs can rival the commercialized silicon solar cells and copper indium gallium selenide (CIGS) solar cells. [2] It is well known that efficient PVSCs require effective suppression of the nonradiative recombination that often originates from nonideal interface energy alignment as well as defects states. [8][9][10][11][12] Charge-transporting materials modification, surface defects passivation, and dimensional engineering are the most adopted strategies to suppress the nonideal interfacial recombination and reduce the energy losses in PVSCs. [13][14][15][16][17][18][19] Among them, the defects at the grain boundaries of 3D perovskite can act as recombination and trapstate centers for minority carriers, which are always considered detrimental to performance. [20] Therefore, the 3D/2D heterojunction architecture stands out as it can simultaneously passivate defects at grain boundaries, modify the interfacial energy alignment, and suppress the ion diffusion, thereby enhancing the device performance and long-term stability. [21][22][23][24][25][26] Currently, most 3D/2D heterostructures are contrived via the modification of perovskite precursor solutions or post-treatment of 3D perovskites. [5,[27][28][29][30][31][32][33][34] For example, Snaith et al. blended butylammonium-based 2D perovskite precursor solution with the cesium formamidinium lead halide perovskite solution to form a mixture of 2D and 3D-phase perovskite, which effectively inhibited nonradiative Perovskite solar cells (PVSCs) have drawn great attention due to their high processability and superior photovoltaic properties. However, their further development is often hindered by severe nonradiative recombination at interfaces that decreases power conversion efficiency (PCE). To this end, a facile strategy to construct a 3D/2D vertical heterostructure to reduce the energy loss in PVSCs is developed. The heterostructure is contrived through the van der Waals integration of 2D perovskite ((BA) 4 AgBiBr 8 ) nanosheets onto the surface of 3D-FAPbI 3 -based perovskites. The large bandgap of (BA) 4 AgBiBr 8 enables the formation of type-I heterojunction with 3D-FAPbI 3 -based perovskites, which serves as a barrier to suppress the trap-assisted recombination at the interface. As a result, a satisfying PCE of 24.48% is achieved with an improved open-circuit voltage (V OC ) from 1.13 to 1.17 V. Moreover, the 2D perovskite nanosheets can effectively mitigate the iodide ion diffusion from perovskite to the metal electrode, hence enhancing the device stability. 3D/2D architectured devices retain ≈90% of their initial PCE under continuous illumination or heating after 1000 h, which are superior to 3D-based devices. This work provides an effective and controllable strategy to construct 3D/2D vertical heterostructure to simultaneously boost the efficiency and stability of PVSCs.