Synergistic Role of Water and Oxygen Leads to Degradation in Formamidinium-Based Halide Perovskites
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Engineering topics
Publications and source records attributed to An, Yu.
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Preferred crystallographic orientation in polycrystalline films is desirable for efficient charge carrier transport in metal halide perovskites and semiconductors. However, the mechanisms that determine the preferred orientation of halide perovskites are still not well understood. In this work, we investigate crystallographic orientation in lead bromide perovskites. We show that the solvent of the precursor solution and organic A-site cation strongly affect the preferred orientation of the deposited perovskite thin films. Specifically, we show that the solvent, dimethylsulfoxide, influences the early stages of crystallization and induces preferred orientation in the deposited films by preventing colloidal particle interactions. Additionally, the methylammonium A-site cation induces a higher degree of preferred orientation than the formamidinium counterpart. We use density functional theory to show that the lower surface energy of the (100) plane facets in methylammonium-based perovskites, compared to the (110) planes, is the reason for the higher degree of preferred orientation. In contrast, the surface energy of the (100) and (110) facets is similar for formamidinium-based perovskites, leading to lower degree of preferred orientation. Furthermore, we show that different A-site cations do not significantly affect ion diffusion in bromine-based perovskite solar cells but impact ion density and accumulation, leading to increased hysteresis. Our work highlights the interplay between the solvent and organic A-site cation which determine crystallographic orientation and plays a critical role in the electronic properties and ionic migration of solar cells.
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The impact of the bulky-cation-modified interfaces on halide perovskite solar cell stability is underexplored. Here, in this work, the thermal instability of the bulky-cation interface layers used in the state-of-the-art solar cells is demonstrated. X-ray photoelectron spectroscopy and synchrotron-based grazing-incidence X-ray scattering measurements reveal significant changes in the chemical composition and structure at the surface of these films that occur under thermal stress. The changes impact charge-carrier dynamics and device operation, as shown in transient photoluminescence, excitation correlation spectroscopy, and solar cells. The type of cation used for surface treatment affects the extent of these changes, where long carbon chains provide more stable interfaces. These results highlight that prolonged annealing of the treated interfaces is critical to enable reliable reporting of performances and to drive the selection of different bulky cations.
Thermal evaporation is a promising deposition technique to scale up perovskite solar cells (PSCs) to large areas, but the lack of understanding of the mechanisms that lead to high-quality evaporated methylammonium lead triiodide (MAPbI 3 ) films gives rise to devices with efficiencies lower than those obtained by spin coating. Here this work investigates the crystalline properties of MAPbI 3 deposited by the thermal coevaporation of PbI 2 and MAI, where the MAI evaporation rate is controlled by setting different temperatures for the MAI source and the PbI 2 deposition rate is controlled with a quartz crystal microbalance (QCM). Using grazing incident wide-angle X-ray scattering (GIWAXS) and X-ray diffraction (XRD), we identify the formation of a secondary orthorhombic phase (with a Pnma space group) that appears at MAI source temperatures below 155 °C. With synchrotron-based X-ray fluorescence (XRF) microscopy, we show that the changes in crystalline phases are not necessarily due to changes in stoichiometry. The films show a stochiometric composition when the MAI source is heated between 140 to 155 °C, and the samples become slightly MAI rich at 165 °C. Increasing the MAI temperature beyond 165 °C introduces an excess of MAI in the film, which promotes the formation of films with low crystallinity that contain low-dimensional perovskites. When they are incorporated in solar cells, the films deposited at 165 °C result in the champion power conversion efficiency, although the presence of a small amount of low-dimensional perovskite may lead to a lower open-circuit voltage. We hypothesize that the formation of secondary phases in evaporated films limits the performance of PSCs and that their formation can be suppressed by controlling the MAI source temperature, bringing the film toward a phase-pure tetragonal structure. Control of the phases during perovskite evaporation is therefore crucial to obtain high-performance solar cells.
The increasing penetration of distributed generations enables an innovative operation paradigm that allows islanded operation to enhance the resilience of the distribution grid. In this study, a cyber-physical oriented islanding strategy is proposed by coordinating centralised and distributed control to achieve seamless islanding transition and operational flexibility in emergency conditions. A cyber-physical control structure is developed to mitigate various disturbances (e.g. emergencies or fluctuations) according to different operation conditions. Specifically, the distributed fault isolation and seamless islanding transition are coordinated to mitigate the outage caused by unplanned islanding, while a secondary control is proposed to support primary control by reducing the power fluctuations during islanded operation. With a rapid response speed, the local cyber-physical devices are coordinated to accomplish islanding separation by selecting a feasible islanded area even under an unplanned islanding situation. A field test was conducted on a practical distribution network in China, and the results demonstrated the effectiveness and feasibility of the proposed islanding strategy.