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The inorganic perovskite CsPbI3 shows promising photophysical properties for a range of potential optoelectronic applications but is metastable at room temperature. To address this, Br can be alloyed into the X-site to create compositions such as CsPbI2Br that are stable at room temperature but have bandgaps >1.9 eV - severely limiting solar applications. Herein, in an effort to achieve phase stable films with bandgaps

An improved understanding of the degradation pathways under external stimuli is needed to address stability challenges in two-dimensional (2D) perovskite semiconductor materials. In this study, in situ synchrotron nanoprobe X-ray fluorescence (nano-XRF) is used to investigate the evolution of halide redistribution within various 2D halide perovskite (n = 1–3) lateral heterostructures under ultraviolet (UV) exposure. The results show that iodine (I) experiences a loss in all cases, with the rate of change following the perovskite dimensionality monotonically. In contrast, bromine (Br) is relatively more stable than I in n = 2 and 3 heterostructures, with no significant change in the total Br concentration but a visible amount of Br diffusion to the previously I-rich regime. Combining nano-XRF and X-ray absorption spectroscopy (XAS), we found a reduction of dimensionality in crystals with n > 1 after UV exposure, indicating significant structural reconfiguration beyond ion migration.

Perovskite solar cells have drawn much attention recently owing to their world-record-setting photovoltaic performances, whereas their practicality is still limited by the structural instability that often arises from ion migration and defect formation. Despite the general understanding that ion instability is a primary cause for degradation, there is no observation of structural transformation at the atomistic scale. Such observation is crucial to understand how instabilities are induced by external perturbations such as illumination or electrical bias, allowing researchers to devise effective strategies to mitigate them. Here, we designed an in situ transmission electron microscopy setup to enable real-time observation of amorphization in perovskite materials under electrical biasing. To reverse the device performance degradation due to such structural changes, the samples were heated at 50 °C and were found to recrystallize, effectively regaining their performance losses. This work presents vital insights on understanding ion-migration phenomena and addressing instability challenges of perovskite optoelectronics.

Degradation due to electron beam exposure has posed a challenge in the use of electron microscopy to probe halide perovskite materials and devices. In this study, the interaction between the electron beam and the perovskite across acceleration voltages and at low probe currents is investigated in a scanning electron microscope (SEM) by monitoring the electron-beam-induced current (EBIC) response in perovskite solar cells in a plan-view configuration. SEM probe conditions are identified where dozens of repeated scans over a single region of the perovskite solar cell induce minimal electronic degradation. Overall, the induced current response of the perovskite device is found to strongly depend upon the beam condition: Rapid decay occurs at high beam powers, the current activates at the lowest beam powers, and a newfound quasi-steady response is revealed at intermediate beam conditions. A quantitative window for the successful conduction of e-beam studies with minimal electronic degradation is revealed by evaluating induced current response over a wide range of perovskite devices, which invites broader use of SEM-based characterization techniques, including EBIC, as powerful techniques for correlative microscopy investigations.

The role of the alkali metal cations in halide perovskite solar cells is not well understood. Using synchrotron-based nano-x-ray fluorescence and complementary measurements, we found that the halide distribution becomes homogenized upon addition of cesium iodide, either alone or with rubidium iodide, for substoichiometric, stoichiometric, and overstoichiometric preparations, where the lead halide is varied with respect to organic halide precursors. Halide homogenization coincides with long-lived charge carrier decays, spatially homogeneous carrier dynamics (as visualized by ultrafast microscopy), and improved photovoltaic device performance. We found that rubidium and potassium phase-segregate in highly concentrated clusters. Alkali metals are beneficial at low concentrations, where they homogenize the halide distribution, but at higher concentrations, they form recombination-active second-phase clusters.

The personal ultraviolet (UV) dosimeter is a useful measurement tool to prevent UV induced dermal damages; however, conventional digital dosimeters are either bulky or require external power sources. Here, a wearable, colorimetric UV film dosimeter that provides color transition, from purple to transparent, is reported to indicate the UV dose. The film dosimeter is made of a purple photodegradable dye ((2Z,6Z)-2,6-bis(2-(2,6-diphenyl-4H-thiopyran-4-ylidene)ethylidene)cyclohexanone or DTEC) blended in low density polyethylene film. The DTEC film discolored 3.3 times more under the exposure of UV light (302 nm) than visible light (543 nm), and a UV bandpass filter is developed to increase this selectivity to UV light. The DTEC film completely discolors to transparency in 2 h under an AM 1.5 solar simulator, suggesting the potential as an indicator for individuals with types I-VI skin to predict interventions to avoid sunburn. Finally, the DTEC film is integrated with the UV bandpass filter on a wristband to function as a wearable dosimeter for low cost and convenient monitoring of sunlight exposure.

A selective C(sp3)−S bond cleavage of thioethers mediated by NBS is developed. Various alkyl bromides have been obtained in good yields using N‐aryl‐3‐(methylthio)propanamides and arylmethylene alkylthioethers. Mechanistic studies suggest that the formation of 3‐bromo‐N‐arylpropanamides may involve sulfoxide intermediates, while the arylmethylene bromides are formed through direct bromination process mediated by NBS. The significance of this strategy lies in its pioneering use of NBS for C−S bond cleavage and subsequent bromination reaction. [ABSTRACT FROM AUTHOR]

Understanding the optoelectronic properties of optically active materials at the nanoscale often proves challenging due to the diffraction-limited resolution of visible light probes and the dose sensitivity of many optically active materials to high-energy electron probes. In this study, we demonstrate correlative synchrotron-based scanning x-ray excited optical luminescence (XEOL) and x-ray fluorescence (XRF) to simultaneously probe local composition and optoelectronic properties of halide perovskite thin films of interest for photovoltaic and optoelectronic devices. We find that perovskite XEOL stability, emission redshifting, and peak broadening under hard x-ray irradiation correlates with trends seen in photoluminescence measurements under continuous visible light laser irradiation. The XEOL stability is sufficient under the intense x-ray probe irradiation to permit proof-of-concept correlative mapping. Typical synchrotron XRF and nano-diffraction measurements use acquisition times 10–100 x shorter than the 5-second acquisition employed for XEOL scans in this study, suggesting that improving luminescence detection should allow correlative XEOL measurements to be performed successfully with minimal material degradation. Analysis of the XEOL emission from the quartz substrate beneath the perovskite reveals its promise for use as a real-time in-situ x-ray dosimeter, which could provide quantitative metrics for future optimization of XEOL data collection for perovskites and other beam-sensitive materials. Overall, the data suggest that XEOL represents a promising route towards improved resolution in the characterization of nanoscale heterogeneities and defects in optically active materials that may be implemented into x-ray nanoprobes to complement existing x-ray modalities. [ABSTRACT FROM AUTHOR]