Advancing of the lead halide perovskite solar cells towards photovoltaic market demands large-scale devices of high-power conversion efficiency, high reproducibility and stability via low-cost fabrication technology, and in particular resistance to humid environment for long-time operation. Here we achieve uniform perovskite film based on a novel polymer-scaffold architecture via a mild-temperature process. These solar cells exhibit efficiency of up to ∼16% with small variation. The unencapsulated devices retain high output for up to 300 h in highly humid environment (70% relative humidity). Moreover, they show strong humidity resistant and self-healing behaviour, recovering rapidly after removing from water vapour. Not only the film can self-heal in this case, but the corresponding devices can present power conversion efficiency recovery after the water vapour is removed. Our work demonstrates the value of cheap, long chain and hygroscopic polymer scaffold in perovskite solar cells towards commercialization.

Ionic transport in organometal halide perovskites is of vital importance because it dominates anomalous phenomena in perovskite solar cells, from hysteresis to switchable photovoltaic effects. However, excited state ionic transport under illumination has remained elusive, although it is essential for understanding the unusual light-induced effects (light-induced self-poling, photo-induced halide segregation and slow photoconductivity response) in organometal halide perovskites for optoelectronic applications. Here, we quantitatively demonstrate light-enhanced ionic transport in CH3NH3PbI3 over a wide temperature range of 17–295 K, which reveals a reduction in ionic transport activation energy by approximately a factor of five (from 0.82 to 0.15 eV) under illumination. The pure ionic conductance is obtained by separating it from the electronic contribution in cryogenic galvanostatic and voltage-current measurements. On the basis of these findings, we design a novel light-assisted method of catalyzing ionic interdiffusion between CH3NH3I and PbI2 stacking layers in sequential deposition perovskite synthesis. X-ray diffraction patterns indicate a significant reduction of PbI2 residue in the optimized CH3NH3PbI3 thin film produced via light-assisted sequential deposition, and the resulting solar cell efficiency is increased by over 100% (7.5%–15.7%) with little PbI2 residue. This new method enables fine control of the reaction depth in perovskite synthesis and, in turn, supports light-enhanced ionic transport.

Due to light-induced effects in CHNH-based perovskites, such as ion migration, defects formation, and halide segregation, the degradation of CHNH-based perovskite solar cells under maximum power point is generally implicated. Here we demonstrated that the effect of light-enhanced ion migration in CHNHPbI can be eliminated by inorganic Cs substitution, leading to an ultrastable perovskite solar cell. Quantitatively, the ion migration barrier for CHNHPbI is 0.62 eV under dark conditions, larger than that of CsPbIBr (0.45 eV); however, it reduces to 0.07 eV for CHNHPbI under illumination, smaller than that for CsPbIBr (0.43 eV). Meanwhile, photoinduced halide segregation is also suppressed in Cs-based perovskites. Cs-based perovskite solar cells retained >99% of the initial efficiency (10.3%) after 1500 h of maximum power point tracking under AM1.5G illumination, while CHNHPbI solar cells degraded severely after 50 h of operation. Our work reveals an uncovered mechanism for stability improvement by inorganic cation substitution in perovskite-based optoelectronic devices.

The fabrication of high-quality perovskite film highly relies on chemical composition and the synthesis method of perovskite. So far, sequentially deposited MA FA Pb(I Br ) polycrystalline film is adopted to produce high-performance perovskite solar cells with record power conversion efficiency (PCE). Fewer grain boundaries and incorporation of inorganic cation (e.g., cesium) would further increase device performance via sequential deposition. Here, cesium chloride (CsCl) is introduced into lead iodide (PbI ) precursor solution that beneficially modulates the property of PbI film, leading to larger grains with cesium incorporation in the resulting perovskite film. The enlarged crystal grains originate from a slower nucleation process for CsCl-containing PbI film when reacting with formamidine iodide, confirmed by in situ confocal photoluminescence imaging. Photovoltaic devices based on CsCl-containing PbI film demonstrate a higher averaging efficiency of 21.3% than 20.3% of the devices without CsCl additives for reverse scan. More importantly, the device stability is improved by CsCl additives that retain over 90% of their initial PCE value after 4000 min tracking at maximum power point under 1-sun illumination. This work paves a way to further improve the photovoltaic performance of mixed-cation-halide perovskite solar cells via a sequential deposition method.

Ion migration has been regarded as the major cause of photocurrent hysteresis. Here we use photoluminescence (PL) and optical images, combined with Galvanostatic measurement, to detect the ionic motion. We observe an irreversible PL and optical transmittance change after electric poling. By comparing a neat perovskite film with the sample coated by poly(methyl methacrylate) (PMMA), polyethylene glycol (PEG), and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), we found that PCBM effectively inhibits ionic motion near the surface of the perovskite.We further evidenced the donor−acceptor complex formed between PCBM and perovskite, implying the mechanism of inhibited ion migration by PCBM. We close by demonstrating that PCBM can also be introduced on the top of perovskite fim in an n−i−p TiO 2 planar structure, to achieve an average 14% steady-state output over 2.3 × 10 5 s (∼64 h). This work highlights the importance of inhibiting ionic motion in perovskite solar cells.

Organometal halide perovskites are mixed electronic−ionic semiconductors. It is imperative to develop a deeper understanding of how ion-migration behavior in perovskites impacts the long-term operational stability of solar cells. In this work, we found that ion penetration from the perovskite layer into the adjacent organic hole-selective layer is a crucial cause of performance degradation in perovskite solar cells. The monovalent cation, namely, methylammonium (MA + ), is the main ion species that penetrates into the organic hole-selective layer of Spiro-MeOTAD because of the built-in electric field during operation. The incorporation of MA + induces deep-level defects in the Spiro-MeOTAD layer and thereby deteriorates the hole-transporting ability of Spiro-MeOTAD, degrading solar cell performance. Our work points to two ways to improve the stability of perovskite solar cells: one is to insert a compact ion-blocking layer between Spiro-MeOTAD and perovskite, and the other is to find a hole-selective layer that is insensitive to extraneous ions (MA + ).

An ideal crystal quality in the grain interior of perovskite polycrystalline films is well recognized; therefore, understanding interfacial impact and the ways to limit interfacial recombination is critical to fabricating highly efficient solar cells. In perovskite solar cells, PbI2 has been used to passivate defects at grain boundaries, yet a systematic PbI2 passivation engineering to boost the high‐performance perovskite solar cells has not been fully explored. Here, a novel device structure comprised of double‐side‐passivated perovskite solar cells (DSPC) is devised through intentionally distributing PbI2 to both the front/rear‐side surfaces and grain boundaries of the formamidinium‐lead‐iodide‐based (FAPbI3‐based) perovskite film. The minority carrier lifetime in double‐side‐passivated perovskite is extended to 1.1 μs with single‐exponential decay using time‐resolved photoluminescence. This result indicates a generic passivation effect of PbI2 on perovskite interfaces, resembling SiO2 passivation in silicon solar cells. Correspondingly, the best photovoltaic device with TiO2‐based planar structure presents a stabilized efficiency of 22%. Moreover, DSPC effectively boosts the limits of open circuit voltages toward a record potential loss of 0.38 V for 1.53 eV‐bandgap perovskites. The architecture of double‐side‐passivated perovskite opens up new opportunities to exceed the efficiency of state‐of‐the‐art perovskite solar cells.

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