Solar cells comprising methylammonium lead iodide perovskite (MAPI) are notorious for their sensitivity to moisture. We show that hydrated crystal phases are formed when MAPI is exposed to water vapour at room temperature and that these phase changes are fully reversed when the material is subsequently dried. The reversible formation of CH 3 NH 3 PbI 3 •H 2 O followed by (CH 3 NH 3 ) 4 PbI 6 •2H 2 O (upon long exposure times) was observed using time resolved XRD and ellipsometry of thin films prepared using 'solvent engineering', single crystals, and state of the art solar cells. In contrast to water vapour, the presence of liquid water results in the irreversible decomposition of MAPI to form PbI 2 . MAPI changes from dark brown to transparent on hydration; the precise optical constants of CH 3 NH 3 PbI 3 •H 2 O formed on single crystals were determined, with a bandgap at 3.1 eV. Using the single crystal optical constants and thin film ellipsometry measurements, the time dependent changes to MAPI films exposed to moisture were modelled. The results suggest that the mono-hydrate phase forms independently of the depth in the film suggesting rapid transport of water molecules along grain boundaries. Vapour phase hydration of an unencapsulated solar cell (initially J sc ≈ 19 mA cm -2 and V oc ≈ 1.05 V at 1 sun) resulted in more than a 90 % drop in short circuit photocurrent and around 200 mV loss in open circuit potential, but these losses were fully reversed after the cell was exposed to dry nitrogen for 6 hours. Hysteresis in the current-voltage characteristics was significantly increased after this dehydration, which may be related to changes in the defect density and morphology of MAPI following recrystallization from the hydrate. Based on our observations we suggest that irreversible decomposition of MAPI in the presence of water vapour only occurs significantly once a grain has been fully converted to the hydrate phase.

Recently developed organic-inorganic hybrid perovskite solar cells combine low-cost fabrication and high power conversion efficiency. Advances in perovskite film optimization have led to an outstanding power conversion efficiency of more than 20%. Looking forward, shifting the focus toward new device architectures holds great potential to induce the next leap in device performance. Here, we demonstrate a perovskite/perovskite heterojunction solar cell. We developed a facile solution-based cation infiltration process to deposit layered perovskite (LPK) structures onto methylammonium lead iodide (MAPI) films. Grazing-incidence wide-angle X-ray scattering experiments were performed to gain insights into the crystallite orientation and the formation process of the perovskite bilayer. Our results show that the self-assembly of the LPK layer on top of an intact MAPI layer is accompanied by a reorganization of the perovskite interface. This leads to an enhancement of the open-circuit voltage and power conversion efficiency due to reduced recombination losses, as well as improved moisture stability in the resulting photovoltaic devices.

We describe the facile synthesis of several two-dimensional covalent–organic frameworks (2D COFs) as films by vapor-assisted conversion at room temperature. High-quality films of benzodithiophene-containing BDT-COF and COF-5 with tunable thickness were synthesized under different conditions on various substrates. BDT-COF films of several micrometer thickness exhibit mesoporosity as well as textural porosity, whereas thinner BDT-COF films materialize as a cohesive dense layer. In addition, we studied the formation of COF-5 films with different solvent mixture compositions serving as vapor source. Room temperature vapor-assisted conversion is an excellent method to form COF films of fragile precursors and on sensitive substrates.

Mobile ions in hybrid perovskite semiconductors introduce a new degree of freedom to electronic devices suggesting applications beyond photovoltaics. An intuitive device model describing the interplay between ionic and electronic charge transfer is needed to unlock the full potential of the technology. We describe the perovskite-contact interfaces as transistors which couple ionic charge redistribution to energetic barriers controlling electronic injection and recombination. This reveals an amplification factor between the out of phase electronic current and the ionic current. Our findings suggest a strategy to design thin film electronic components with large, tuneable, capacitor-like and inductor-like characteristics. The resulting simple equivalent circuit model, which we verified with time-dependent drift-diffusion simulations of measured impedance spectra, allows a general description and interpretation of perovskite solar cell behaviour. Broader contextHighly efficient solar cells made using hybrid perovskite semiconductors may prove commercially viable. The success of these cheap materials is in part due to their ability to I.G., D.M. and P.B. initiated the project led by P.B. D.M. measured devices fabricated and developed by M.S., O.G., H.H., D.L. and P.D.; I.G. performed the simulations on software developed with P.C.; D.M. and P.B. developed the transistor description and circuit models; W.F. and D.M. performed the equivalent circuit fitting using circuit models coded by P.B. All authors discussed the results and participated in preparation of the manuscript drafted by P.B, D.M. I.G. and P.C.

Adding cesium (Cs) and rubidium (Rb) cations to FA0.83MA0.17Pb(I0.83Br0.17)3 hybrid lead halide perovskites results in a remarkable improvement in solar cell performance, but the origin of the enhancement has not been fully understood yet. In this work, Time-of-Flight (ToF), Time-Resolved Microwave Conductivity (TRMC), and Thermally Stimulated Current (TSC) measurements were performed to elucidate the impact of the inorganic cation additives on the trap landscape and charge transport properties within perovskite solar cells. These complementary techniques allow for the assessment of both local features within the perovskite crystals and macroscopic properties of films and full devices. Strikingly, Cs-incorporation was shown to reduce the trap density and charge recombination rates in the perovskite layer. This is consistent with the significant improvements in the open-circuit voltage and fill factor of Cscontaining devices. By comparison, Rb-addition results in an increased charge carrier mobility, which is accompanied by a minor increase in device efficiency and reduced current-voltage hysteresis. By mixing Cs and Rb in quadruple cation (Cs-Rb-FA-MA) perovskites, the advantages of both inorganic cations can be combined. Our study provides valuable insights into the role of these additives in multiple-cation perovskite solar cells, which are essential for the design of highperformance devices.

Methylammonium lead iodide (MAPbI3) perovskite based solar cells have recently emerged as a serious competitor for large scale and low-cost photovoltaic technologies. However, since these solar cells contain toxic lead, a sustainable procedure for handling the cells after their operational lifetime is required to prevent exposure of the environment to lead and to comply with international electronic waste disposal regulations. Herein, we report a procedure to remove every layer of the solar cells separately, which gives the possibility to selectively isolate the different materials. Besides isolating the toxic lead iodide in high yield, we show that the PbI2 can be reused for the preparation of new solar cells with comparable performance and in this way avoid lead waste. Furthermore, we show that the most expensive part of the solar cell, the conductive glass (FTO), can be reused several times without any reduction in the performance of the devices. With our simple recycling procedure, we address both the risk of contamination and the waste disposal of perovskite based solar cells while further reducing the cost of the system. This brings perovskite solar cells one step closer to their introduction into commercial systems.

Rubidium and cesium cations have been recently identified as enhancers for perovskite solar cell performance. However, the impact of these inorganic cations on the stability of the (FA0.83MA0.17)­Pb­(I0.83Br0.17)3 perovskite crystal lattice has not been fully understood yet. Here, we show via in situ X-ray diffraction and energy-dispersive X-ray spectrometry measurements that the unsuitably small ionic radius of Rb+ can lead to several nonphotoactive side-products. During the perovskite film synthesis, RbPb­(I1–x Br x )3 is formed, while exposure to humid air leads to the rapid formation of another hitherto unreported side phase (RbPb2I4Br). The formation of the Rb-rich side phases not only results in a loss of light absorption but also extracts bromide ions from the photoactive perovskite phase, thereby reducing its band gap. In comparison, the moisture-assisted formation of a CsPb2I4Br phase upon Cs-addition occurs on a significantly longer time scale than its Rb analog. While the incorporation of Cs+ remains attractive for high-performance solar cells, the severe moisture-sensitivity of Rb-containing mixed-halide perovskites may create additional engineering challenges.

We investigated the influence of moisture on CH3NH3PbI3 perovskite films and solar cells derived from non-stoichiometric precursor mixtures. We followed both the structural changes under controlled air humidity via in-situ X-ray diffraction, and the electronic behavior of devices prepared from these films. A small PbI2 excess in the films improved the stability of the perovskite compared to stoichiometric samples. We assign this to excess PbI2 layers at the perovskite grain boundaries or to the termination of the perovskite crystals with lead and iodine. In contrast, the MAI-excess films composed of smaller perovskite crystals showed increased electronic disorder and reduced device performance due to poor charge collection. Upon exposure to moisture followed by dehydration ("solvent annealing"), these films recrystallized to form larger, highly oriented crystals with fewer electronic defects and a remarkable improvement in photocurrent and photovoltaic efficiency.