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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]

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]

Correlative X‐ray microscopy, including synchrotron X‐ray diffraction and fluorescence, is leveraged to understand the local role of europium as a B‐site additive in CsPbBr3 perovskite crystals. Europium addition reduces microstrain in the perovskite, despite the fact that the degree of europium incorporation into the perovskite varies locally, with a maximum loading over twice the nominal stoichiometry. The presence of europium improves photoluminescence yield and bandwidth, while shifting the emission to bluer wavelengths. Finally, europium‐containing crystals have greatly improved X‐ray hardness. The findings show promise for europium as an additive in perovskite optoelectronic devices. [ABSTRACT FROM AUTHOR]

Lead halide perovskites are among the most exciting classes of optoelectronic materials due to their unique ability to form high‐quality crystals with tunable bandgaps in the visible and near‐infrared using simple solution precipitation reactions. This facile crystallization is driven by their ionic nature; just as with other salts, it is challenging to form amorphous halide perovskites, particularly in thin‐film form where they can most easily be studied. Here, rapid desolvation promoted by the addition of acetate precursors is shown as a general method for making amorphous lead halide perovskite films with a wide variety of compositions, including those using common organic cations (methylammonium and formamidinium) and anions (bromide and iodide). By controlling the amount of acetate, it is possible to tune from fully crystalline to fully amorphous films, with an interesting intermediate state consisting of crystalline islands embedded in an amorphous matrix. The amorphous lead halide perovskite has a large and tunable optical bandgap. It improves the photoluminescence quantum yield and lifetime of incorporated crystalline perovskite, opening up the intriguing possibility of using amorphous perovskite as a passivating contact, as is currently done in record efficiency silicon solar cells. [ABSTRACT FROM AUTHOR]

Abstract: Hybrid organometal halide perovskites are known for their excellent optoelectronic functionality as well as their wide‐ranging chemical flexibility. The composition of hybrid perovskite devices has trended toward increasing complexity as fine‐tuned properties are pursued, including multielement mixing on the constituents A and B and halide sites. However, this tunability presents potential challenges for charge extraction in functional devices. Poor consistency and repeatability between devices may arise due to variations in composition and microstructure. Within a single device, spatial heterogeneity in composition and phase segregation may limit the device from achieving its performance potential. This review details how the nanoscale elemental distribution and charge collection in hybrid perovskite materials evolve as chemical complexity increases, highlighting recent results using nondestructive operando synchrotron‐based X‐ray nanoprobe techniques. The results reveal a strong link between local chemistry and charge collection that must be controlled to develop robust, high‐performance hybrid perovskite materials for optoelectronic devices. [ABSTRACT FROM AUTHOR]

The light-emitting diodes (LEDs) used in indoor testing of perovskite solar cells do not expose them to the levels of ultraviolet (UV) radiation that they would receive in actual outdoor use. We report degradation mechanisms of p-i-n–structured perovskite solar cells under unfiltered sunlight and with LEDs. Weak chemical bonding between perovskites and polymer hole-transporting materials (HTMs) and transparent conducting oxides (TCOs) dominate the accelerated A-site cation migration, rather than direct degradation of HTMs. An aromatic phosphonic acid, [2-(9-ethyl-9H-carbazol-3-yl)ethyl]phosphonic acid (EtCz3EPA), enhanced bonding at the perovskite/HTM/TCO region with a phosphonic acid group bonded to TCOs and a nitrogen group interacting with lead in perovskites. A hybrid HTM of EtCz3EPA with strong hole-extraction polymers retained high efficiency and improved the UV stability of perovskite devices, and a champion perovskite minimodule—independently measured by the Perovskite PV Accelerator for Commercializing Technologies (PACT) center—retained operational efficiency of >16% after 29 weeks of outdoor testing. [ABSTRACT FROM AUTHOR]

Correlative X‐ray microscopy, including synchrotron X‐ray diffraction and fluorescence, is leveraged to understand the local role of europium as a B‐site additive in CsPbBr3 perovskite crystals. Europium addition reduces microstrain in the perovskite, despite the fact that the degree of europium incorporation into the perovskite varies locally, with a maximum loading over twice the nominal stoichiometry. The presence of europium improves photoluminescence yield and bandwidth, while shifting the emission to bluer wavelengths. Finally, europium‐containing crystals have greatly improved X‐ray hardness. The findings show promise for europium as an additive in perovskite optoelectronic devices. [ABSTRACT FROM AUTHOR]

Spatial heterogeneities in the chemical makeup of thin film photovoltaic devices are pivotal in determining device efficiency. We report the in-plane spatial distribution and degree of chlorine incorporation in organic-inorganic lead halide perovskite absorbers by means of nondestructive synchrotron-based nanoprobe X-ray fluorescence. The presence of chlorine is positively identified in CH3NH3PbI3 films synthesized with Cl-containing precursors and as an impurity in some films synthesized with nominally Cl-free precursors. The impurity may be introduced from precursors or as contaminants during film synthesis. The films formed from Cl-containing precursors contain roughly an order of magnitude higher amount of chlorine, with Cl:I values greater than 0.02 found whether Cl is present in either the organic or the inorganic precursor for both one- and two-step fabrication processes. A spatial variation in the Cl incorporation is observed within single particles and as well as between particles within a given film, and the standard deviation of the Cl:I ratio across the films is up to 30% of the average value. Understanding and controlling the heterogeneous distribution of chlorine in hybrid perovskite layers may offer a path to improve their photovoltaic performance. [ABSTRACT FROM AUTHOR]