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The development of highly stable and efficient wide-bandgap (WBG) perovskite solar cells (PSCs) based on bromine-iodine (Br–I) mixed-halide perovskite (with Br greater than 20%) is critical to create tandem solar cells. However, issues with Br–I phase segregation under solar cell operational conditions (such as light and heat) limit the device voltage and operational stability. This challenge is often exacerbated by the ready defect formation associated with the rapid crystallization of Br-rich perovskite chemistry with antisolvent processes. We combined the rapid Br crystallization with a gentle gas-quench method to prepare highly textured columnar 1.75–electron volt Br–I mixed WBG perovskite films with reduced defect density. With this approach, we obtained 1.75–electron volt WBG PSCs with greater than 20% power conversion efficiency, approximately 1.33-volt open-circuit voltage ( V oc ), and excellent operational stability (less than 5% degradation over 1100 hours of operation under 1.2 sun at 65°C). When further integrated with 1.25–electron volt narrow-bandgap PSC, we obtained a 27.1% efficient, all-perovskite, two-terminal tandem device with a high V oc of 2.2 volts.

Achieving the long-term stability of perovskite solar cells is arguably the most important challenge required to enable widespread commercialization. Understanding the perovskite crystallization process and its direct impact on device stability is critical to achieving this goal. The commonly employed dimethyl-formamide/dimethyl-sulfoxide solvent preparation method results in a poor crystal quality and microstructure of the polycrystalline perovskite films. In this work, we introduce a high-temperature dimethyl-sulfoxide-free processing method that utilizes dimethylammonium chloride as an additive to control the perovskite intermediate precursor phases. By controlling the crystallization sequence, we tune the grain size, texturing, orientation (corner-up versus face-up) and crystallinity of the formamidinium (FA)/caesium (FA)yCs1–yPb(IxBr1–x)3 perovskite system. A population of encapsulated devices showed improved operational stability, with a median T80 lifetime (the time over which the device power conversion efficiency decreases to 80% of its initial value) for the steady-state power conversion efficiency of 1,190 hours, and a champion device showed a T80 of 1,410 hours, under simulated sunlight at 65 °C in air, under open-circuit conditions. This work highlights the importance of material quality in achieving the long-term operational stability of perovskite optoelectronic devices.

Deciphering the atomic and electronic structures of interfaces is key to developing state-of-the-art perovskite semiconductors. However, conventional characterization techniques have limited previous studies mainly to grain-boundary interfaces, whereas the intragrain-interface microstructures and their electronic properties have been much less revealed. Herein using scanning transmission electron microscopy, we resolved the atomic-scale structural information on three prototypical intragrain interfaces, unraveling intriguing features clearly different from those from previous observations based on standalone films or nanomaterial samples. These intragrain interfaces include composition boundaries formed by heterogeneous ion distribution, stacking faults resulted from wrongly stacked crystal planes, and symmetrical twinning boundaries. The atomic-scale imaging of these intragrain interfaces enables us to build unequivocal models for the ab initio calculation of electronic properties. Our results suggest that these structure interfaces are generally electronically benign, whereas their dynamic interaction with point defects can still evoke detrimental effects. This work paves the way toward a more complete fundamental understanding of the microscopic structure–property–performance relationship in metal halide perovskites.

Here, we describe a model of C3, C3–C4 intermediate, and C4 photosynthesis that is designed to facilitate quantitative analysis of physiological measurements. The model relates the factors limiting electron transport and carbon metabolism, the regulatory processes that coordinate these metabolic domains, and the responses to light, carbon dioxide, and temperature. It has three unique features. First, mechanistic expressions describe how the cytochrome b6f complex controls electron transport in mesophyll and bundle sheath chloroplasts. Second, the coupling between the mesophyll and bundle sheath expressions represents how feedback regulation of Cyt b6f coordinates electron transport and carbon metabolism. Third, the temperature sensitivity of Cyt b6f is differentiated from that of the coupling between NADPH, Fd, and ATP production. Using this model, we present simulations demonstrating that the light dependence of the carbon dioxide compensation point in C3–C4 leaves can be explained by co-occurrence of light saturation in the mesophyll and light limitation in the bundle sheath. We also present inversions demonstrating that population-level variation in the carbon dioxide compensation point in a Type I C3–C4 plant, Flaveriachloraefolia, can be explained by variable allocation of photosynthetic capacity to the bundle sheath. These results suggest that Type I C3–C4 intermediate plants adjust pigment and protein distributions to optimize the glycine shuttle under different light and temperature regimes, and that the malate and aspartate shuttles may have originally functioned to smooth out the energy supply and demand associated with the glycine shuttle. This model has a wide range of potential applications to physiological, ecological, and evolutionary questions.

Reliable spatiotemporal crop data are vital for sustainable agricultural management. However, efficient algorithms that can be automatically applied to large regions are scarce, especially for cash...

Assessing the prognostic utility of lymph node status in pediatric rhabdomyosarcoma (RMS) patients and identifying demographic and clinical predictors of positive lymph node status among pediatric rhabdomyosarcoma patients.Retrospective cohort study of head and neck RMS in patients with and without positive lymph node metastasis.National Cancer Database (NCDB) was queried for patients of young (0-11 years) and adolescent (12-21 years) ages with head and neck RMS and confirmed positive or negative lymph node metastasis status. Descriptive analyses, Kaplan-Meier survival analyses, and multivariate logistic regressions were performed on extracted demographic and clinical characteristics.Among 272 head and neck RMS patients, 146 (54%) were found to have positive lymph node metastasis. Alveolar RMS (n = 147, 54%) followed by embryonal RMS (n = 74, 27%) were the most represented histology types. Positive lymph node metastasis conferred significantly decreased survivability (p 0.001) with a median survival period of 36.42 months compared to negative lymph node metastasis with a period of 53.47 months. Older age showed markedly increased odds (OR-2.02; 95%CI 1.22-3.38) of having lymph node metastasis when controlling for sex, race, insurance status, and Charlson-Comorbidity score. Alveolar histologies showed markedly increased odds of having lymph node metastasis (OR-3.21; 95%CI 1.96-5.31); embryonal histologies showed markedly decreased odds of having lymph node metastasis (OR-0.32; 95%CI 0.18-0.56) CONCLUSIONS: This study highlights the significant prognostic value of lymph node status among pediatric head and neck rhabdomyosarcoma patients while showcasing crucial demographic and pathological predictors of lymph node metastasis in said patients. Use of lymph node status in pediatric head and neck rhabdomyosarcoma will present future steps towards improving its clinical course.

Metal halide perovskites (MHPs) combine extraordinary optoelectronic properties with chemical and mechanical properties not found in their semiconductor counterparts. For instance, they exhibit optoelectronic properties on par with single-crystalline gallium arsenide yet exhibit near-zero formation energies. The small lattice energy of MHPs means they undergo a rich diversity of polymorphism near standard conditions similar to organic materials. MHPs also demonstrate ionic transport as high as state-of-the-art battery electrodes. The most widespread applications for metal halide perovskites (e.g. photovoltaics and solid-state lighting) typically view low formation energies, polymorphism, and high ion transport as a nuisance that should be eliminated. Here, we put these properties into perspective by comparing them to other technologically relevant semiconductors in order to highlight how unique this combination of properties is for semiconductors and to illustrate ways to leverage these properties in emerging applications.

We provide here an overview of the remarkable life and outstanding research of David (Dave) Charles Fork (March 4, 1929-December 13, 2021) in oxygenic photosynthesis. In the words of the late Jack Edgar Myers, he was a top 'photosynthetiker'. His research dealt with novel findings on light absorption, excitation energy distribution, and redistribution among the two photosystems, electron transfer, and their relation to dynamic membrane change as affected by environmental changes, especially temperature. David was an attentive listener and a creative designer of experiments and instruments, and he was also great fun to work with. He is remembered here by his family, coworkers, and friends from around the world including Australia, France, Germany, Japan, Sweden, Israel, and USA.

In 2013, the FDA placed a black box warning on the usage of opioid pain medications in the post-operative setting after pediatric adenotonsillectomy. Since then, alternative pain management regimens have been employed. Some have advocated for post-operative oral steroids, in part due to the effectiveness of intraoperative intravenous steroids in reducing post-operative pain and nausea. The evidence regarding the efficacy and safety of post-operative oral steroids is not as clear. The purpose of this study was to examine whether post-tonsillectomy hemorrhage rates in pediatric patients were affected by post-operative oral steroid usage.Case-control retrospective chart review using a deidentified data set of patients undergoing tonsillectomy with or without adenoidectomy at a single academic medical center between June 2012 and November 2015.A total of 1416 patients were included in the study, with 704 in the no post-operative oral steroids group and 712 in the group who did receive post-operative oral steroids. The rate of post-tonsillectomy hemorrhage in the post-operative oral steroid group was 3.1 % compared to 1.8 % in the group who did not receive post-operative oral steroids, however, this was not a statistically significant difference (P = .132).Our study suggests that post-operative oral steroids are safe and do not increase the risk of post-operative hemorrhage after pediatric tonsillectomy.

Here, we present a conceptual and quantitative model to describe the role of the Cytochrome $$\hbox {b}_{6}\hbox {f}$$ b 6 f complex in controlling steady-state electron transport in $$\hbox {C}_{3}$$ C 3 leaves. The model is based on new experimental methods to diagnose the maximum activity of Cyt $$\hbox {b}_{6}\hbox {f}$$ b 6 f in vivo, and to identify conditions under which photosynthetic control of Cyt $$\hbox {b}_{6}\hbox {f}$$ b 6 f is active or relaxed. With these approaches, we demonstrate that Cyt $$\hbox {b}_{6}\hbox {f}$$ b 6 f controls the trade-off between the speed and efficiency of electron transport under limiting light, and functions as a metabolic switch that transfers control to carbon metabolism under saturating light. We also present evidence that the onset of photosynthetic control of Cyt $$\hbox {b}_{6}\hbox {f}$$ b 6 f occurs within milliseconds of exposure to saturating light, much more quickly than the induction of non-photochemical quenching. We propose that photosynthetic control is the primary means of photoprotection and functions to manage excitation pressure, whereas non-photochemical quenching functions to manage excitation balance. We use these findings to extend the Farquhar et al. (Planta 149:78–90, 1980) model of $$\hbox {C}_{3}$$ C 3 photosynthesis to include a mechanistic description of the electron transport system. This framework relates the light captured by PS I and PS II to the energy and mass fluxes linking the photoacts with Cyt $$\hbox {b}_{6}\hbox {f}$$ b 6 f , the ATP synthase, and Rubisco. It enables quantitative interpretation of pulse-amplitude modulated fluorometry and gas-exchange measurements, providing a new basis for analyzing how the electron transport system coordinates the supply of Fd, NADPH, and ATP with the dynamic demands of carbon metabolism, how efficient use of light is achieved under limiting light, and how photoprotection is achieved under saturating light. The model is designed to support forward as well as inverse applications. It can either be used in a stand-alone mode at the leaf-level or coupled to other models that resolve finer-scale or coarser-scale phenomena.

Summary Polycrystalline photovoltaic materials offer low costs and good scalability; however, grain boundaries in these materials are extended defects, which can drastically increase carrier recombination. Interestingly, three leading polycrystalline thin-film technologies—cadmium telluride (CdTe), CuIn1-xGaxSe2 (CIGS), and perovskite solar cells (PSCs)—passivate absorber surfaces in the same way: via formation of low-dimensional, typically two-dimensional (2D), van der Waals materials. This has primarily occurred serendipitously through process optimization, but in some cases, 2D capping layers are intentionally incorporated to improve device performance. Here, evidence compiled from the literature, supplemented with new data where necessary, is presented to illustrate the existence of 3D/2D interfaces in CdTe, CIGS, and PSCs, and their correlation with improved passivation and device performance. This suggests that 3D/2D passivation might be a heretofore unappreciated key to successful polycrystalline thin-film photovoltaics. Finally, the desired attributes of successful low-dimensional layers are presented with rational design strategies for next-generation polycrystalline solar cells.

Summary The development of mixed tin-lead (Sn-Pb)-based perovskite solar cells (PSCs) with low band gap (1.2–1.4 eV) has become critical not only for pushing single-junction devices toward the maximum efficiency given by the Shockley-Queisser limit, but also for enabling all-perovskite tandem devices beyond this limit. However, achieving high power-conversion efficiency (PCE) and long-term device operation stability simultaneously remains a significant challenge for Sn-Pb-based PSCs. Here, we demonstrate near ideal-band-gap (∼1.34 eV) methylammonium-free Sn-Pb-based PSCs with high efficiency (∼20%) and promising operational stability of maintaining >80% of initial PCE over 750 h under maximum-power-point tracking. The key to this success is the use of a SnCl2⋅3FACl complex additive that improves the microstructure and reduces the development of residual stress in the Sn-Pb perovskite thin films, which in turn enhances the efficiency and stability of the Sn-Pb-based ideal-band-gap PSCs.

While research on derivatives of both bulk and low-dimensional metal halide perovskite (MHP) semiconductors has grown exponentially over the past decade, the understanding and intentional applicati...

Summary Surface modification of organic-inorganic halide perovskite thin films represents a promising approach to enhance the efficiency and stability of perovskite solar cells. Here, we synthesized N-methyl-1,3-propane diammonium diiodide (Me-PDAI2) and found that Me-PDA2+ can template a three-dimensional “perovskitoid” structure (Me-PDA)Pb2I6. Simple surface treatment with Me-PDAI2 on top of a standard (FAPbI3)0.85(MAPbI2Br)0.10(CsPbI3)0.05 perovskite induces the formation of a thin (Me-PDA)Pb2I6 perovskitoid surface layer, leading to smoother surface texture, longer charge-carrier lifetime, higher charge-carrier mobility, and a reduced surface-defect density. With the perovskitoid surface modification, the device efficiency is significantly improved from 20.3% to 22.0% along with enhanced stability in both shelf life (ISOS-D-1 stability) and operation (ISOS-L-1 stability). We further demonstrated that the perovskitoid surface engineering approach is applicable to various perovskite compositions, including CsFAMA-, FAMA-, and MA-based lead halide perovskites, making perovskitoid an important design motif for perovskite surface engineering for enhanced device performance and stability.

Remote sensing of solar-induced fluorescence (SIF) opens a new window for quantifying a key ecological variable, the terrestrial ecosystem gross primary production (GPP), because of the revealed strong SIF-GPP correlation. However, similar to many other remotely sensed metrics, SIF observations suffer from the sun-sensor geometry effects, which may have important impacts on the SIF-GPP relationship but remain poorly understood. Here we used remotely sensed SIF, globally distributed tower GPP data, and a mechanistic model to provide a systematic analysis. Our results reveal that leaf physiology, canopy structure, and sun-sensor geometries all affect the SIF-GPP relationship. In particular, we found that SIF observations in the sun-tracking hotspot direction can be a better proxy of GPP due to the similar responses of light use efficiency and SIF escaping probability in the hotspot direction to the increasing incoming solar radiation. Such conclusions are supported by a variety of modeling simulations and satellite observations over various plant function types, at different time scales and with satellite observational modes. This study demonstrates the potential and advantage of normalizing SIF observations to the hotspot direction for better global GPP estimations. This study also demonstrates the great potentials of current and future spaceborne sun-tracking satellite missions for a significant improvement in measuring and monitoring, at a wide range of spatial and temporal scales, the changes in terrestrial ecosystem GPP in response to anticipated changes in the Earth's environmental conditions.

Greening represents a significant increase in vegetation activity. Accurate quantification of global greening in peak growth is vital for quantifying changes in terrestrial productivity. Normalized Difference Vegetation Index (NDVI) is the remote sensing indicator most commonly applied for this purpose. However, there is limited knowledge about how the applications of other improved or newly available products can impact global greening assessments. This study reports the first systematic investigation of the impact of vegetation indicator selection on global greening in peak growth. It examines the period from 2003 to 2017 using six indicators with a spatial resolution of 500 m: Near Infrared Reflectance of terrestrial vegetation (NIRv) and the coupled diagnostic biophysical modeled Gross Primary Production (PML-GPP), together with NDVI, Enhanced Vegetation Index with two bands (EVI2), Leaf Area Index (LAI) and Moderate Resolution Imaging Spectroradiometer (MODIS) GPP (MOD-GPP) calculated based on MODIS images. Vegetation trends were estimated using the Mann–Kendall test, the unanimous trends by six vegetation indicators were derived, and the concordance ratio in estimated trends by each pair of indicators was investigated among different biomes and their sensitivity to changes in climate were investigated. We found that the estimated greening and browning varied between 12–23% and 2–13% of the vegetated areas, respectively. There was more net greening estimated from NDVI and MOD-GPP (around 19%) compared to the other indicators (8–11%). The concordance ratio between EVI2 and NIRv was much higher (>94%) than other combinations (61–76%) at the global scale. The concordance ratio between one specific indicator and the other indicators gradually increased with its change magnitude. Unanimous results from these six indicators were exhibited in less than two-fifths (38.71%) of vegetated areas. Apart from the EVI2 and NIRv, the concordance ratio varied among different biomes: high in cropland (67–81%), but low in deciduous needle-leaf forest (51–62%) and very low in evergreen broadleaf forest between PML-GPP and others (37–49%). The diverse sensitivity to changes in climate contributed to the discrepancies: greening was more pronounced during warming conditions for the GPP products when compared with the greenness indices. At the global scale, the concordance ratio was higher during cooling conditions among all the indicators except between PML-GPP. Datasets supporing these findings are available online at https://github.com/FuzhouSIRC/Greening_6indicators.2

Summary Inorganic perovskite solar cells (PSCs) are promising for achieving long-term operational stability with good device performance. Here, we report the fabrication of inorganic CsPbI2Br-based perovskite thin films with a well-defined CsPbI3−xBrx composition gradient in the surface region by a scalable, orthogonal processable spray-coating approach. The graded structure broadens absorption wavelength range and increases carrier lifetime, but it also causes electrical field redistribution within a device stack for more efficient charge separation and collection. With this approach, we obtained a power conversion efficiency of 16.81% for a 0.096-cm2 PSC. We further demonstrated a monolithically integrated perovskite submodule based on the graded CsPbI3−xBrx by spray coating with an efficiency of 13.82% (112-cm2 aperture area) and ∼9% degradation over 1,000-h continuous 1-sun light soaking.

Cost-effective, high-throughput industrial applications of metal-halide perovskites require a highly tolerant method (i.e., wide process window) that produces high-quality materials with a short an...

Using time-resolved in situ X-ray photoelectron spectroscopy, we identify and suppress rapid degradation mechanisms for cesium-stabilized formamidinium lead iodide perovskite materials used in stat...