Halide perovskites are found to exhibit strain patterns over large areas, which influences the lifetimes of charge carriers.
Do corals form their skeletons by precipitation from solution or by attachment of amorphous precursor particles as observed in other minerals and biominerals? The classical model assumes precipitation in contrast with observed “vital effects,” that is, deviations from elemental and isotopic compositions at thermodynamic equilibrium. Here, we show direct spectromicroscopy evidence in Stylophora pistillata corals that two amorphous precursors exist, one hydrated and one anhydrous amorphous calcium carbonate (ACC); that these are formed in the tissue as 400-nm particles; and that they attach to the surface of coral skeletons, remain amorphous for hours, and finally, crystallize into aragonite (CaCO3). We show in both coral and synthetic aragonite spherulites that crystal growth by attachment of ACC particles is more than 100 times faster than ion-by-ion growth from solution. Fast growth provides a distinct physiological advantage to corals in the rigors of the reef, a crowded and fiercely competitive ecosystem. Corals are affected by warming-induced bleaching and postmortem dissolution, but the finding here that ACC particles are formed inside tissue may make coral skeleton formation less susceptible to ocean acidification than previously assumed. If this is how other corals form their skeletons, perhaps this is how a few corals survived past CO2 increases, such as the Paleocene–Eocene Thermal Maximum that occurred 56 Mya.
The exploration of the synthetic space of halide perovskites hinges on an enormous number of parameters requiring time-consuming experimentation to decouple and optimize. Here, the formation of the prototype material CH 3 NH 3 PbI 3 (MAPbI 3 ) is investigated at different time and length scales using multimodal in situ measurements to monitor the evolution of crystalline phases, morphology, and photoluminescence as a function of the lead precursors. Kinetically fast formation of crystalline precursor phases already during the spin-coat deposition is observed using lead iodide (PbI 2 ) or lead chloride (PbCl 2 ) routes. These precursor phases most likely template final MAPbI 3 film morphology. In particular, the emergence of the "needle-like" structure is shown to appear before film annealing. In situ photoluminescence measurements suggest nanoscale nucleation followed by rapid nuclei densification and growth. Using this multimodal in situ approach, different formation pathways can be identified either via precursor phases in the PbI 2 and PbCl 2 routes or direct perovskite formation from molecular building blocks as observed in the lead acetate (PbAc 2 ) route. Correlation of in situ results with photovoltaic device performance demonstrates the power of in situ multimodal techniques, paves the way to a fast screening of synthetic parameters, and ultimately leads to controlled synthetic procedures that yield high-efficiency devices.
Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. Here, we shed light on photoinduced halide demixing using insitu photoluminescence spectroscopy and synchrotron Xray diffraction (XRD) to directly compare the evolution of composition and phase changes in CH(NH 2 ) 2 CsPbhalide (FACsPb) and CH 3 NH 3 Pbhalide (MAPb) perovskites upon illumination, thereby providing insights into why FACsPbhalides are less prone to halide demixing than MAPbperovskites. We find that halide demixing occurs in both materials.However, the formed Irich domains accumulate strain for the case of FACsPbperovskites but readily relax for the case of MAPbperovskites. The accumulated strain energy is expected to act as a stabilizing force against halide demixing and may explain the higher Br composition threshold for demixing to occur in FACsPbhalides. In addition, we find that while halide demixing leads to a quenching of the high energy photoluminescence emission from MA 2 perovskites, the emission is enhanced for the case of FaCsperovskites. This behavior points to a reduction of nonradiative recombination centers in FACsperovskites arising from the demixing process. FACsPbhalide perovskites exhibit excellent intrinsic material properties, with photoluminescence quantum yields that are comparable to MAperovskites. Since improved stability is achieved without sacrificing electronic properties, these compositions are better candidates for photovoltaic applications, especially as wide bandgap absorbers in tandem cells. , and high photoluminescence quantum yields 2,4 . Their general crystal structure is described by ABX 3 , typically comprising a monovalent organic cation A (e.g. Despite the importance of overcoming halide demixing for achieving stable perovskitebased photovoltaic devices, there remains uncertainty about the underlying mechanism(s) and most studies have focused on MAperovskites. Currently, strain or carrierinduced lattice distortion, 6 compositional inhomogeneity, 7 defectmediated halide migration, 6,8,9 and crystal domain size 10 are actively considered as contributing to halide segregation. In particular, Bischak et al. propose that halide demixing is a consequence of localized strain generated from the interaction of charge carriers with the lattice (polaron formation). 6In this respect, they find that the combination of 4 mobile halides, long charge carrier lifetimes, and significant electronphonon coupling are prerequisites for halide demixing. 6 In a different study, Barker et al. suggest that defectassisted halide ion migration away from the illuminated surface, with a slower hopping rate of iodide and a potential dependence on charge carrier generation gradients, results in formation of Irich regions at the surface. In this explanation, they argue that halide segregation in a single cr...
Complex phenomena are prevalent during the formation of materials, which affect their processing-structure-function relationships. Thin films of methylammonium lead iodide (CH3NH3PbI3, MAPI) are processed by spin coating, antisolvent drop, and annealing of colloidal precursors. The structure and properties of transient and stable phases formed during the process are reported, and the mechanistic insights of the underlying transitions are revealed by combining in situ data from grazing-incidence wide-angle X-ray scattering and photoluminescence spectroscopy. Here, we report the detailed insights on the embryonic stages of organic-inorganic perovskite formation. The physicochemical evolution during the conversion proceeds in four steps: i) An instant nucleation of polydisperse MAPI nanocrystals on antisolvent drop, ii) the instantaneous partial conversion of metastable nanocrystals into orthorhombic solvent-complex by cluster coalescence, iii) the thermal decomposition (dissolution) of the stable solvent-complex into plumboiodide fragments upon evaporation of solvent from the complex and iv) the formation (recrystallization) of cubic MAPI crystals in thin film.
Composite multiferroic systems, consisting of a piezoelectric substrate coupled with a ferromagnetic thin film, are of great interest from a technological point of view because they offer a path toward the development of ultralow power magnetoelectric devices. The key aspect of those systems is the possibility to control magnetization via an electric field, relying on the magneto-elastic coupling at the interface between the piezoelectric and the ferromagnetic components. Accordingly, a direct measurement of both the electrically induced magnetic behavior and of the piezo-strain driving such behavior is crucial for better understanding and further developing these materials systems. In this work, we measure and characterize the micron-scale strain and magnetic response, as a function of an applied electric field, in a composite multiferroic system composed of 1 and 2 μm squares of Ni fabricated on a prepoled [Pb(MgNb)O]-[PbTiO] (PMN-PT) single crystal substrate by X-ray microdiffraction and X-ray photoemission electron microscopy, respectively. These two complementary measurements of the same area on the sample indicate the presence of a nonuniform strain which strongly influences the reorientation of the magnetic state within identical Ni microstructures along the surface of the sample. Micromagnetic simulations confirm these experimental observations. This study emphasizes the critical importance of surface and interface engineering on the micron-scale in composite multiferroic structures and introduces a robust method to characterize future devices on these length scales.
We present the strain and temperature dependence of an anomalous nematic phase in optimally doped BaFe_{2}(As,P)_{2}. Polarized ultrafast optical measurements reveal broken fourfold rotational symmetry in a temperature range above T_{c} in which bulk probes do not detect a phase transition. Using ultrafast microscopy, we find that the magnitude and sign of this nematicity vary on a 50-100 μm length scale, and the temperature at which it onsets ranges from 40 K near a domain boundary to 60 K deep within a domain. Scanning Laue microdiffraction maps of local strain at room temperature indicate that the nematic order appears most strongly in regions of weak, isotropic strain. These results indicate that nematic order arises in a genuine phase transition rather than by enhancement of local anisotropy by a strong nematic susceptibility. We interpret our results in the context of a proposed surface nematic phase.
Silicon is considered as a promising anode material for the next-generation lithium-ion battery (LIB) due to its high capacity at nanoscale. However, silicon expands up to 300% during lithiation, which induces high stresses and leads to fractures. To design silicon nanostructures that could minimize fracture, it is important to understand and characterize stress states in the silicon nanostructures during lithiation. Synchrotron X-ray microdiffraction has proven to be effective in revealing insights of mechanical stress and other mechanics considerations in small-scale crystalline structures used in many important technological applications, such as microelectronics, nanotechnology, and energy systems. In the present study, an in situ synchrotron X-ray microdiffraction experiment was conducted to elucidate the mechanical stress states during the first electrochemical cycle of lithiation in single-crystalline silicon nanowires (SiNWs) in an LIB test cell. Morphological changes in the SiNWs at different levels of lithiation were also studied using scanning electron microscope (SEM). It was found from SEM observation that lithiation commenced predominantly at the top surface of SiNWs followed by further progression toward the bottom of the SiNWs gradually. The hydrostatic stress of the crystalline core of the SiNWs at different levels of electrochemical lithiation was determined using the in situ synchrotron X-ray microdiffraction technique. We found that the crystalline core of the SiNWs became highly compressive (up to -325.5 MPa) once lithiation started. This finding helps unravel insights about mechanical stress states in the SiNWs during the electrochemical lithiation, which could potentially pave the path toward the fracture-free design of silicon nanostructure anode materials in the next-generation LIB.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.