The existence of a defective area composed of nanocrystals and amorphous phases on a perovskite film inevitably causes nonradiative charge recombination and structural degradation in perovskite photovoltaics. In this study, a stoichiometric etching strategy for the top surface of a defective cesium lead halide perovskite is developed by using ionic liquids. The dissolution of the original defective area substantially exposes the underlying perovskite, which is a high‐quality surface with retained stoichiometry and lattice continuity. The ionic liquid molecules are adsorbed on the perovskite surface via Coulombic interactions and passivate the undercoordinated surface lead centers. Such a structural modulation considerably reduces the trap density of the perovskite devices and enables a record power conversion efficiency of 17.51% and an open‐circuit voltage of 1.37 V of the CsPbI2Br cell with a perovskite bandgap of 1.88 eV. This work provides a novel technical route to improve the efficiency and environmental resilience of perovskite‐based optoelectronic devices.

Metal halide perovskite (MHP) is an emerging class of semiconducting materials with superior optoelectronic properties, which have achieved notable success in photoelectric device applications. As a classical technique for semiconductor...

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Passivation, as a classical surface treatment technique, has been widely accepted in start-of-the-art perovskite solar cells (PSCs) that can effectively modulate the electronic and chemical property of defective perovskite surface. The discovery of inorganic passivation compounds, such as oxysalts, has largely advanced the efficiency and lifetime of PSCs on account of its favorable electrical property and remarkable inherent stability, but a lack of deep understanding of how its local configuration affects the passivation effectiveness is a huge impediment for future interfacial molecular engineering. Here, we demonstrate the central-atom-dependent-passivation of oxysalt on perovskite surface, in which the central atoms of oxyacid anions dominate the interfacial oxygen-bridge strength. We revealed that the balance of local interactions between the central atoms of oxyacid anions (e.g., N, C, S, P, Si) and the metal cations on perovskite surface (e.g., Pb) generally determines the bond formation at oxysalt/perovskite interface, which can be understood by the bond order conservation principle. Silicate with less electronegative Si central atoms provides strong O-Pb motif and improved passivation effect, delivering a champion efficiency of 17.26% for CsPbI2Br solar cells. Our strategy is also universally effective in improving the device performance of several commonly used perovskite compositions.

The insertion of organic spacers into halide perovskite slabs has offered a trade-off between the efficiency and stability of perovskite solar cells (PSCs). The layered structure of diammonium-intercalated cesium lead halide perovskites is virtually unexplored, in contrast to several works on the monoammonium system. In this report, we find that perovskite with 1,4-butanediammonium (BDA) and cesium cations can only form n = 1 and n = 2 layered isologues defined by the chemical formula of (BDA)­Cs n–1Pb n (I0.7Br0.3)3n+1, while the n = 3–4 ones will self-construct into unique heterostructures comprising separated quantum wells (QWs; n = 1–2) and 3D (n = ∞) perovskites. We highlight that the 2D/3D heterostructures show a structural resemblance to that of bulk heterojunction in organics, thus improving the charge separation and transport more than surface passivation. Solar cells based on the (BDA)­Cs3Pb4I9.1Br3.9 (n = 4) absorbing layer delivered a power conversion efficiency (PCE) reaching 9.49% with ideal light and thermal stability.

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Understanding the degradation mechanism of perovskite solar cells (PSCs) is of particular importance to solve their instability issue, which is one of the major hindrances toward commercialization. Here, it is shown that a halide diffusion equilibrium exists at the heterointerface of perovskite devices, which strongly impacts the evolution of device performance. The combined experimental and theoretical studies reveal that halide components diffuse from perovskite to fullerene layers in a p‐i‐n PSC device and equilibrate with an iodine density of 1018–1019 cm−3 within 80 h under dark aging condition. It is found that there is a strong correction between the device efficiency and halide diffusion equilibrium of PSCs, as the diffused halides can chemically dope the transport layer and result in the nonstoichiometric perovskite surface, leading to both initial enhancement and long‐term loss of the photovoltaic efficiency of solar cells. In response to this issue, a predoping strategy is developed to attain the halide diffusion equilibrium once the device is fabricated, thereby avoiding the further halide migration and initial efficiency variations. As a result, the as‐prepared PSC achieved an efficiency of 23.13% as well as stable power output under continuous one sun illumination.

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