Perfluorinated Self Assembled Monolayers Enhance the Stability and Efficiency of Inverted Perovskite Solar Cells

Perovskite solar cells are among the most exciting photovoltaic systems as they combine low recombination losses, ease of fabrication, and high spectral tunability. The Achilles heel of this technology is the device stability due to the ionic nature of the perovskite crystal, rendering it highly hygroscopic, and the extensive diffusion of ions especially at increased temperatures. Herein, we demonstrate the application of a simple solution-processed perfluorinated self-assembled monolayer (p-SAM) that not only enhances the solar cell efficiency, but also improves the stability of the perovskite absorber and, in turn, the solar cell under increased temperature or humid conditions. The p-i-n-type perovskite devices employing these SAMs exhibited power conversion efficiencies surpassing 21%. Notably, the best performing devices are stable under standardized maximum power point operation at 85 °C in inert atmosphere (ISOS-L-2) for more than 250 h and exhibit superior humidity resilience, maintaining ∼95% device performance even if stored in humid air in ambient conditions over months (∼3000 h, ISOS-D-1). Our work, therefore, demonstrates a strategy towards efficient and stable perovskite solar cells with easily deposited functional interlayers

Synchronous Versus Metachronous Metastatic Disease: Impact of Time to Metastasis on Patient Outcome-Results from the International Metastatic Renal Cell Carcinoma Database Consortium

BACKGROUND: Patients with metastatic renal cell carcinoma (mRCC) may present with primary metastases (synchronous disease) or develop metastases during follow-up (metachronous disease). The impact of time to metastasis on patient outcome is poorly characterised. OBJECTIVE: To characterise overall survival (OS) and time to treatment failure (TTF) based on time to metastasis in mRCC patients treated with targeted therapy (tyrosine kinase inhibitors [TKIs]). DESIGN, SETTING, AND PARTICIPANTS: We used the International Metastatic Renal Cell Carcinoma Database Consortium (IMDC) to compare synchronous (metastases within ≤3 mo of initial diagnosis of cancer) versus metachronous disease (evaluated by >3-12 mo, >1-2 yr, >2-7 yr, and >7 yr intervals). OUTCOME MEASUREMENTS AND STATISTICAL ANALYSIS: OS and TFF were assessed using Kaplan-Meier curves. Cox multivariable regressions analyses (MVAs) were adjusted for baseline factors. RESULTS AND LIMITATIONS: Of 7386 patients with mRCC treated with first-line TKIs, 3906 (53%) and 3480 (47%) had synchronous and metachronous metastasis, respectively. More patients with synchronous versus metachronous disease had higher T stage (T1-2: 19% vs 34%), N1 disease (21% vs 6%), presence of sarcomatoid differentiation (15.8% vs 7.9%), Karnofsky performance status <80 (25.9% vs 15.1%), anaemia (62.5% vs 42.3%), elevated neutrophils (18.9% vs 10.9%), elevated platelets (21.6% vs 11.4%), bone metastases (40.4% vs 29.8%), and IMDC poor risk (40.6% vs 11.3%). Synchronous versus metachronous disease by intervals >3-12 mo, >1-2 yr, >2-7 yr, and >7 yr correlated with poor TTF (5.6 mo vs 7.3, 8.0, 10.8, and 13.3 mo, p <  0.0001) and poor OS (median 16.7 mo vs 23.8, 30.2, 34.8, and 41.7 mo, p <  0.0001). In MVAs, the adjusted hazard ratios (95% confidence intervals) were 1.00 (reference), 0.98 (0.90-1.06), 0.81 (0.73-0.91), 0.74 (0.68-0.81), and 0.60 (0.54-0.67), respectively, for OS (p <  0.0001), and 1.00 (reference), 0.99 (0.92-1.06), 0.98 (0.90-1.07), 0.83 (0.77-0.89), and 0.66 (0.60-0.72), respectively, for TTF (p <  0.0001). Data were collected retrospectively. CONCLUSIONS: Timing of metastases after initial RCC diagnosis may impact the outcomes from targeted therapy in mRCC. PATIENT SUMMARY: We looked at the impact of the timing of metastatic outbreak on survival outcomes in kidney cancer patients treated with targeted therapy. We found that the longer time to metastatic development was associated with improved outcome. Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved

Apatite : a new redox proxy for silicic magmas?

The oxidation states of magmas provide valuable information about the release and speciation of volatile elements during volcanic eruptions, metallogenesis, source rock compositions, open system magmatic processes, tectonic settings and potentially titanium (Ti) activity in chemical systems used for Ti-dependent geothermometers and geobarometers. In this paper we explore the use of Mn in apatite as an oxybarometer in intermediate and silicic igneous rocks. Increased Mn concentrations in apatite in granitic rocks from the zoned Criffell granitic pluton (southern Scotland) correlate with decreasing Fe2O3 (Fe3+) and Mn in the whole-rock and likely reflect increased Mn2+/Mn3+ and greater compatibility of Mn2+ relative to Mn3+ in apatite under reduced conditions. Fe3+/Fe2+ ratios in biotites have previously been used to calculate oxygen fugacities (fO2) in the outer zone granodiorites and inner zone granites where redox conditions have been shown to change from close to the magnetite-hematite buffer to close to the nickel-nickel oxide buffer respectively ( Stephens et al., 1985). This trend is apparent in apatite Mn concentrations from a range of intermediate to silicic volcanic rocks that exhibit varying redox states and are shown to vary linearly and negatively with log fO2, such that logfO2=-0.0022(±0.0003)Mn(ppm)-9.75(±0.46)logfO2=-0.0022(±0.0003)Mn(ppm)-9.75(±0.46) Variations in the Mn concentration of apatites appear to be largely independent of differences in the Mn concentration of the melt. Apatite Mn concentrations may therefore provide an independent oxybarometer that is amenable to experimental calibration, with major relevance to studies on detrital mineral suites, particularly those containing a record of early Earth redox conditions, and on the climatic impact of historic volcanic eruptions