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Abstract Metal halide perovskites based on formamidinium (FA), or FA‐rich compositions have shown great promise for high‐performance photovoltaics. A deeper understanding of the impact of ambient conditions (e.g., moisture, oxygen, and illumination) on the possible reactions of FA‐based perovskite films and their processing sensitivities has become critical for further advances toward commercialization. Herein, we investigate reactions that take place on the surface of the FA0.7Cs0.3, mixed Br/I wide bandgap perovskite thin films in the presence of humid air and ambient illumination. The treatment forms a surface layer containing O, OH, and N‐based anions. We propose the latter originates from formamidine trapped at the perovskite/oxide interface reacting further to cyanide and/or formamidinate—an understudied class of pseudohalides that bind to Pb. Optimized treatment conditions improve photoluminescence quantum yield owing to both reduced surface recombination velocity and increased bulk carrier lifetime. The corresponding perovskite solar cells also exhibit improved performance. Identifying these reactions opens possibilities for better utilizing cyanide and amidinate ligands, species that may be expected during vapor processing of FA‐based perovskites. Our work also provides new insights into the self‐healing or self‐passivating of MA‐free perovskite compositions where FA and iodide damage could be partially offset by advantageous reaction byproducts. imagemore » « lessFree, publicly-accessible full text available February 1, 2026
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Although C60is usually the electron transport layer (ETL) in inverted perovskite solar cells, its molecular nature of C60leads to weak interfaces that lead to non-ideal interfacial electronic and mechanical degradation. Here, we synthesized an ionic salt from C60, 4-(1',5′-dihydro-1'-methyl-2'H-[5,6] fullereno-C60-Ih-[1,9-c]pyrrol-2'-yl) phenylmethanaminium chloride (CPMAC), and used it as the electron shuttle in inverted PSCs. The CH2-NH3+head group in the CPMA cation improved the ETL interface and the ionic nature enhanced the packing, leading to ~3-fold increase in the interfacial toughness compared to C60. Using CPMAC, we obtained ~26% power conversion efficiencies (PCEs) with ~2% degradation after 2,100 hours of 1-sun operation at 65°C. For minimodules (four subcells, 6 centimeters square), we achieved the PCE of ~23% with <9% degradation after 2,200 hours of operation at 55°C.more » « less
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Solar-induced chlorophyll fluorescence (SIF) is widely accepted as a proxy for gross primary productivity (GPP). Among the various SIF measurements, tower-based SIF measurements allow for continuous monitoring of SIF variation at a canopy scale with high temporal resolution, making it suitable for monitoring highly variable plant physiological responses to environmental changes. However, because of the strong and close relationship between SIF and absorbed photosynthetically active radiation (aPAR), it may be difficult to detect the influence of environmental drivers other than light conditions. Among the drivers, atmospheric dryness (vapor pressure deficit, VPD) is projected to increase as drought becomes more frequent and severe in the future, negatively impacting plants. In this study, we evaluated the tower-based high-frequency SIF measurement as a tool for detecting plant response to highly variable VPD. The study was performed in a mixed temperate forest in Virginia, USA, where a 40-m-tall flux tower has been measuring gas and energy exchanges and ancillary environmental drivers, and the Fluospec 2 system has been measuring SIF. We show that a proper definition of light availability to vegetation can reproduce SIF response to changing VPD that is comparable to GPP response as estimated from eddy covariance measurement: GPP decreased with rising VPD regardless of how aPAR was defined, whereas SIF decreased only when aPAR was defined as the PAR absorbed by chlorophyll (aPARchl) or simulated by a model (Soil Canopy Observation, Photochemistry and Energy fluxes, SCOPE). We simulated the effect of VPD on SIF with two different simulation modes of fluorescence emission representing contrasting moisture conditions, ‘Moderate’ and ‘Soil Moisture (SM) Stress’ modes. The decreasing SIF to rising VPD was only found in the SM Stress mode, implying that the SIF-VPD relationship depends on soil moisture conditions. Furthermore, we observed a similar response of SIF to VPD at hourly and daily scales, indicating that satellite measurements can be used to study the effects of environmental drivers other than light conditions. Finally, the definition of aPAR emphasizes the importance of canopy structure research to interpret remote sensing observations properly.more » « less
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Mechanical failure and chemical degradation of device heterointerfaces can strongly influence the long-term stability of perovskite solar cells (PSCs) under thermal cycling and damp heat conditions. We report chirality-mediated interfaces based onR-/S-methylbenzyl-ammonium between the perovskite absorber and electron-transport layer to create an elastic yet strong heterointerface with increased mechanical reliability. This interface harnesses enantiomer-controlled entropy to enhance tolerance to thermal cycling–induced fatigue and material degradation, and a heterochiral arrangement of organic cations leads to closer packing of benzene rings, which enhances chemical stability and charge transfer. The encapsulated PSCs showed retentions of 92% of power-conversion efficiency under a thermal cycling test (−40°C to 85°C; 200 cycles over 1200 hours) and 92% under a damp heat test (85% relative humidity; 85°C; 600 hours).more » « less
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Aerosols can affect photosynthesis through radiative perturbations such as scattering and absorbing solar radiation. This biophysical impact has been widely studied using field measurements, but the sign and magnitude at continental scales remain uncertain. Solar-induced fluorescence (SIF), emitted by chlorophyll, strongly correlates with photosynthesis. With recent advancements in Earth observation satellites, we leverage SIF observations from the Tropospheric Monitoring Instrument (TROPOMI) with unprecedented spatial resolution and near-daily global coverage, to investigate the impact of aerosols on photosynthesis. Our analysis reveals that on weekends when there is more plant-available sunlight due to less particulate pollution, 64% of regions across Europe show increased SIF, indicating more photosynthesis. Moreover, we find a widespread negative relationship between SIF and aerosol loading across Europe. This suggests the possible reduction in photosynthesis as aerosol levels increase, particularly in ecosystems limited by light availability. By considering two plausible scenarios of improved air quality—reducing aerosol levels to the weekly minimum 3-d values and levels observed during the COVID-19 period—we estimate a potential of 41 to 50 Mt net additional annual CO2uptake by terrestrial ecosystems in Europe. This work assesses human impacts on photosynthesis via aerosol pollution at continental scales using satellite observations. Our results highlight i) the use of spatiotemporal variations in satellite SIF to estimate the human impacts on photosynthesis and ii) the potential of reducing particulate pollution to enhance ecosystem productivity.more » « less
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