We have identified an often observed yet unresolved intermediate structure in a popular processing with dimethylformamide solutions of lead chloride and methylammonium iodide for perovskite solar cells. With subsecond time-resolved grazing-incidence X-ray scattering and X-ray photoemission spectroscopy, supplemental with ab initio calculation, the resolved intermediate structure (CHNH)PbICl·CHNHI features two-dimensional (2D) perovskite bilayers of zigzagged lead-halide octahedra and sandwiched CHNHI layers. Such intermediate structure reveals a hidden correlation between the intermediate phase and the composition of the processing solution. Most importantly, the 2D perovskite lattice of the intermediate phase is largely crystallographically aligned with the [110] planes of the three-dimensional perovskite cubic phase; consequently, with sublimation of Cl ions from the organo-lead octahedral terminal corners in prolonged annealing, the zigzagged octahedral layers of the intermediate phase can merge with the intercalated methylammonium iodide layers for templated growth of perovskite crystals. Regulated by annealing temperature and the activation energies of the intermediate and perovskite, deduced from analysis of temperature-dependent structural kinetics, the intermediate phase is found to selectively mature first and then melt along the layering direction for epitaxial conversion into perovskite crystals. The unveiled epitaxial conversion under growth kinetics controls might be general for solution-processed and intermediate-templated perovskite formation.
Recently, a new seeding growth approach for perovskite thin films is reported to significantly enhance the device performance of perovskite solar cells. This work unveils the intermediate structures and the corresponding growth kinetics during conversion to perovskite crystal thin films assisted by seeding PbS nanocrystals (NCs), using time-resolved grazing-incidence X-ray scattering. Through analyses of time-resolved crystal formation kinetics obtained from synchrotron X-rays with a fast subsecond probing time resolution, an important "catalytic" role of the seed-like PbS NCs is clearly elucidated. The perovskite precursor-capped PbS NCs are found to not only accelerate the nucleation of a highly oriented intermediate phase, but also catalyze the conversion of the intermediate phase into perovskite crystals with a reduced activation energy E a = 47 (±5) kJ mol −1 , compared to 145 (±38) kJ mol −1 for the pristine perovskite thin film. The reduced E a is attributed to a designated crystal lattice alignment of the perovskite nanocrystals with perovskite cubic crystals; the pivotal heterointerface alignment of the perovskite crystals coordinated by the Pb NCs leads to an improved film surface morphology with less pinholes and enhanced crystal texture and thermal stability. These together contribute to the significantly improved photovoltaic performance of the corresponding devices.
Summary A thin‐profile buckling‐restrained brace (thin‐BRB) consists of a rectangular steel casing and a flat steel core that is parallel to a gusset plate. A thin configuration reduces the width of the restraining member and thus saves usable space in buildings. However, deformable debonding layers, which cover the steel core plate in order to mitigate the difference between the peak tensile and compressive axial forces, provide a space for the steel core to form high mode buckling waves when the thin‐BRB is under compression. The wave crests squeeze the debonding layers and produce outward forces on the inner surface of the restraining member. If the restraining member is too weak in sustaining the outward forces, local bulging failure occurs and the thin‐BRB loses its compression capacity immediately. In order to investigate local bulging behavior, a total of 22 thin‐BRB specimens with a ratio of steel core plate to restraining steel tube depth ranging from 0.3 to 0.7 and axial yield force capacities ranging from 421 kN to 3036 kN were tested by applying either cyclically increasing, decreasing, or constant axial strains. The restraining steel tube widths of all the specimens were smaller than 200 mm and were infilled with mortar with a compressive strength of 97 MPa or 55 MPa. Thirteen of the 22 thin‐BRB specimens' restraining members bulged out when the compressive core strains exceeded 0.03. A seismic design method of the thin‐BRB in preventing local bulging failure is proposed in this study. Test and finite element model (FEM) analysis results suggest that the outward forces can be estimated according to the BRB compressive strength, steel core high mode buckling wavelength, and the debonding layer thickness. In addition, the capacity of the restraining member in resisting the outward forces can be estimated by using the upper bound theory in plastic analysis. Both the FEM analysis and test results indicate that the proposed method is effective in predicting the possibility of local bulging failure. Test results indicate that the proposed design method is conservative for thin‐BRB specimens with a large steel core plate to restraining steel tube depth ratio. This paper concludes with design recommendations for thin‐BRBs for severe seismic services. Copyright © 2015 John Wiley & Sons, Ltd.
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