The high polarity of water molecules inevitably causes the decomposition of perovskites. We retard the degradation by introducing an ultrathin ALD–Al2O3layer, which has almost no negative effect on performance.

Flexible perovskite solar cells (f‐PSCs) have attracted great attention because of their unique advantages in lightweight and portable electronics applications. However, their efficiencies are far inferior to those of their rigid counterparts. Herein, a novel histamine diiodate (HADI) is designed based on theoretical study to modify the SnO2/perovskite interface. Systematic experimental results reveal that the HADI serves effectively as a multifunctional agent mainly in three aspects: 1) surface modification to realign the SnO2 conduction band upward to improve interfacial charge extraction; 2) passivating the buried perovskite surface, and 3) bridging between the SnO2 and perovskite layers for effective charge transfer. Consequently, the rigid MA‐free PSCs based on the HADI‐SnO2 electron transport layer (ETL) display not only a high champion power conversion efficiency (PCE) of 24.79% and open‐circuit voltage (VOC) of 1.20 V but also outstanding stability as demonstrated by the PSCs preserving 91% of their initial efficiencies after being exposed to ambient atmosphere for 1200 h without any encapsulation. Furthermore, the solution‐processed HADI‐SnO2 ETL formed at low temperature (100 °C) is utilized in f‐PSCs that achieve a PCE as high as 22.44%, the highest reported PCE for f‐PSCs to date.

Perovskite solar cells based on two-dimensional/three-dimensional (2D/3D) hierarchical structure have attracted significant attention in recent years due to their promising photovoltaic performance and stability. However, obtaining a detailed understanding of interfacial mechanism at the 2D/3D heterojunction, for example, the ligand-chemistrydependent nature of the 2D/3D heterojunction and its influence on charge collection and the final photovoltaic outcome, is not yet fully developed. Here we demonstrate the underlying 3D phase templates growth of quantum wells (QWs) within a 2D capping layer, which is further influenced by the fluorination of spacers and compositional engineering in terms of thickness distribution and orientation. Better QW alignment and faster dynamics of charge transfer at the 2D/3D heterojunction result in higher charge mobility and lower charge recombination loss, largely explaining the significant improvements in charge collection and open-circuit voltage (V OC ) in complete solar cells. As a result, 2D/3D solar cells with a power-conversion efficiency of 21.15% were achieved, significantly higher than the 3D counterpart (19.02%). This work provides key missing information on how interfacial engineering influences the desirable electronic properties of the 2D/3D hierarchical films and device performance via ligand chemistry and compositional engineering in the QW layer.

The unstable feature of the widely employed organic hole‐transporting materials (HTMs) (e.g., spiro‐MeOTAD) significantly limits the practical application of perovskite solar cells (PSCs). Therefore, it is desirable to design new structured PSCs with stable HTMs presenting excellent carrier extraction and transfer properties. This work demonstrates a new inverted PSC configuration. The new PSC has a graded band alignment and bilayered inorganic HTMs (i.e., compact NiOx and mesoporous CuGaO2). In comparison with planar‐structured PSCs, the mesoporous CuGaO2 can effectively extract holes from perovskite due to the increased contact area of the perovskite/HTM. The graded energy alignment constructed in the ultrathin compact NiOx, mesoporous CuGaO2, and perovskite can facilitate carrier transfer and depress charge recombination. As a result, the champion device based on the newly designed mesoscopic PSCs yields a stabilized efficiency of ≈20%, which is considered one of the best results for inverted PSCs with inorganic HTMs. Additionally, the unencapsulated PSC device retains more than 80% of its original efficiency when subjected to thermal aging at 85 °C for 1000 h in a nitrogen atmosphere, thus demonstrating superior thermal stability of the device. This study may pave a new avenue to rational design of highly efficient and stable PSCs.

All-inorganic CsPbI 3 perovskite presents preeminent chemical stability and a desirable band gap as the front absorber for perovskite/silicon tandem solar cells. Unfortunately, CsPbI 3 perovskite solar cells (PSCs) still show low efficiency due to high density of defects in solution-prepared CsPbI 3 films. Herein, three kinds of hydrazide derivatives (benzoyl hydrazine (BH), formohydrazide (FH) and benzamide (BA)) are designed to reduce the defect density and stabilize the phase of CsPbI 3 . Calculation and characterization results corroborate that the carboxyl and hydrazine groups in BH form strong chemical bonds with Pb 2 + ions, resulting in synergetic double coordination. In addition, the hydrazine group in the BH also forms a hydrogen bond with iodine to assist the coordination. Consequently, a high efficiency of 20.47 % is achieved, which is the highest PCE among all pure CsPbI 3 -based PSCs reported to date. In addition, an unencapsulated device showed excellent stability in ambient air.Since a cesium lead iodide (CsPbI 3 ) perovskite solar cell (PSC) was first reported in 2015, CsPbI 3 perovskite has attracted great interest due to its excellent chemical stability and appropriate band gap ( � 1.7 eV) as the front sub-cell active layer for tandem solar cells. [1][2][3] Regrettably, the highest power conversion efficiency (PCE) of CsPbI 3 -based