The power conversion efficiency of perovskite solar cells (PSCs) has ascended from 3.8% to 22.1% in recent years. ZnO has been well-documented as an excellent electron-transport material. However, the poor chemical compatibility between ZnO and organo-metal halide perovskite makes it highly challenging to obtain highly efficient and stable PSCs using ZnO as the electron-transport layer. It is demonstrated in this work that the surface passivation of ZnO by a thin layer of MgO and protonated ethanolamine (EA) readily makes ZnO as a very promising electron-transporting material for creating hysteresis-free, efficient, and stable PSCs. Systematic studies in this work reveal several important roles of the modification: (i) MgO inhibits the interfacial charge recombination, and thus enhances cell performance and stability; (ii) the protonated EA promotes the effective electron transport from perovskite to ZnO, further fully eliminating PSCs hysteresis; (iii) the modification makes ZnO compatible with perovskite, nicely resolving the instability of ZnO/perovskite interface. With all these findings, PSCs with the best efficiency up to 21.1% and no hysteresis are successfully fabricated. PSCs stable in air for more than 300 h are achieved when graphene is used to further encapsulate the cells.

During the past two years, the introduction of DMSO has revolutionized the fabrication of high-quality pervoskite MAPbI3 (MA = CH3NH3) films for solar cell applications. In the developed DMSO process, the formation of (MA)2Pb3I8·2DMSO (shorted as Pb3I8) has well recognized as a critical factor to prepare high-quality pervoskite films and thus accomplish excellent performances in perovskite solar cells. However, Pb3I8 is an I-deficient intermediate and must further react with methylammonium iodide (MAI) to be fully converted into MAPbI3. By capturing and solving the molecular structures of several intermediates involved in the fabrication of perovskite films, we report in this work that the importance of DMSO is NOT due to the formation of Pb3I8. The use of different PbI2-DMSO ratios leads to two different structures of PbI2-DMSO precursors (PbI2·DMSO and PbI2·2DMSO), thus dramatically influencing the quality of fabricated perovskite films. However, such an influence can be minimized when the PbI2-DMSO precursor films are thermally treated to create mesoporous PbI2 films before reacting with MAI. Such a development makes the fabrication of high-quality pervoskite films highly reproducible without the need to precisely control the PbI2:DMSO ratio. Moreover, the formation of ionic compound (MA)4PbI6 is observed when excess MAI is used in the preparation of perovskite film. This I-rich phase heavily induces the hysteresis in PSCs, but is readily removed by isopropanol treatment. On the basis of all these findings, we develop a new effective protocol to fabricate high-performance PSCs. In the new protocol, high-quality perovskite films are prepared by simply treating the mesoporous PbI2 films (made from PbI2-DMSO precursors) with an isopropanol solution of MAI, followed by isopropanol washing. The best efficiency of fabricated MAPbI3 PSCs is up to 19.0%. As compared to the previously reported DMSO method, the devices fabricated by the method reported in this work display narrow efficiency distributions in both forward and reverse scans. And the efficiency difference between forward and reverse scans is much smaller.

Perovskite solar cells (PSCs) have reached certified efficiencies of up to 23.7% but suffered from frailness and instability when exposed to ambient atmosphere. Zinc oxide (ZnO), when used as electron transport layer (ETL) on PSCs, gives rise to excellent electronic, optic, and photonic properties, yet the Lewis basic nature of ZnO surface leads to deprotonation of the perovskite layer, resulting in serious degradation of PSCs using ZnO as ETL. Here, we report a simple but effective strategy to convert ZnO surface into ZnS at the ZnO/perovskite interface by sulfidation. The sulfide on ZnO–ZnS surface binds strongly with Pb2+ and creates a novel pathway of electron transport to accelerate electron transfer and reduce interfacial charge recombination, yielding a champion efficiency of 20.7% with improved stability and no appreciable hysteresis. The model devices modified with sulfide maintained 88% of their initial performance for 1000 h under storage condition and 87% for 500 h under UV radiation. ZnS is demonstrated to act as both a cascade ETL and a passivating layer for enhancing the performance of PSCs.

Efficient control of crystallization and defects of perovskite films are the key factors toward the performance and stability of perovskite solar cells (PSCs), especially for the preparation of large-area PSCs devices. Herein, we directly embedded surfactant-like monoammonium zinc porphyrin (ZnP) compound into the methylammonium (MA+) lead iodide perovskite film to blade-coat large-area uniform perovskite films as large as 16 cm2. Efficiency as high as 18.3% for blade-coating large-area (1.96 cm2) PSCs with ZnP was unprecedentedly achieved, while the best efficiency of fabricated small-area (0.1 cm2) device was up to 20.5%. The detailed analyses demonstrated the functions of ZnP in crystallization control and defects passivation of perovskite surfaces and grain boundaries. As a consequence, the ZnP-encapsulated devices retained over 90% of its initial efficiency after 1000 h with a humidity of about 45% at 85 °C. This research presents a facile way to achieve the synergistic effect of large-area coating, morphology tailoring, and defect suppression based on the molecular encapsulation strategy for perovskite films, further improving the photovoltaic performance and stability of PSCs.