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At least 163 records · Page 9

Early- and late-time dynamics of laser-produced plasmas by combining emission and absorption spectroscopy

Optical emission spectroscopy and laser absorption spectroscopy are two highly complementary techniques for diagnosing plasmas, specifically in the determination of important parameters such as temperature and density. In this work, we characterized a laser-produced plasma by combining emission and tunable absorption spectroscopy. Plasmas are produced by focusing pulses from a frequency quadrupled Nd:YAG laser onto a glass target containing a minor concentration of aluminum in an ambient atmosphere of ~100 Torr N 2 . Here, emission spectroscopy is used to investigate the line behavior of Al and Ca, electron density, and excitation temperature at times = 5 μs, while absorption spectroscopy is used to investigate the line behavior of Al and Ca, species density, and kinetic temperature at times = 5-100 μs. A comparison is made between the excitation temperature measured from emission using the Boltzmann plot method and the kinetic temperature measured from absorption; the implications of this comparison on local thermodynamic equilibrium and line-of-sight averaging are discussed. By combining the two methods of optical emission and laser absorption spectroscopy, a comprehensive characterization of the plasma over the entire lifetime of its evolution is possible, leading to a greater understanding of the plasma behavior including particle condensation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Control of Host-Matrix Morphology Enables Efficient Deep-Blue Organic Light-Emitting Devices

Mixing a sterically bulky, electron-transporting host material into a conventional single host–guest emissive layer is demonstrated to suppress phase separation of the host matrix while increasing the efficiency and operational lifetime of deep-blue phosphorescent organic light-emitting diodes (PHOLEDs) with chromaticity coordinates of (0.14, 0.15). Here, the bulky host enables homogenous mixing of the molecules comprising the emissive layer while suppressing single host aggregation; a significant loss channel of nonradiative recombination. By controlling the amorphous phase of the host-matrix morphology, the mixed-host device achieves a significant reduction in nonradiative exciton decay, resulting in 120 ± 6% increase in external quantum efficiency relative to an analogous, single-host device. In contrast to single host PHOLEDs where electrons are transported by the host and holes by the dopants, both charge carriers are conducted by the mixed host, reducing the probability of exciton annihilation, thereby doubling of the deep-blue PHOLED operational lifetime. These findings demonstrate that the host matrix morphology affects almost every aspect of PHOLED performance.

36 MATERIALS SCIENCE↗

Early retirement of power plants in climate mitigation scenarios

International efforts to avoid dangerous climate change aim for large and rapid reductions of fossil fuel CO 2 emissions worldwide, including nearly complete decarbonization of the electric power sector. However, achieving such rapid reductions may depend on early retirement of coal- and natural gas-fired power plants. Here, we analyze future fossil fuel electricity demand in 171 energy-emissions scenarios from Integrated Assessment Models (IAMs), evaluating the implicit retirements and/or reduced operation of generating infrastructure. Although IAMs calculate retirements endogenously, the structure and methods of each model differ; we use a standard approach to infer retirements in outputs from all six major IAMs and—unlike the IAMs themselves—we begin with the age distribution and region-specific operating capacities of the existing power fleet. We find that coal-fired power plants in scenarios consistent with international climate targets (i.e. keeping global warming well-below 2 °C or 1.5 °C) retire one to three decades earlier than historically has been the case. If plants are built to meet projected fossil electricity demand and instead allowed to operate at the level and over the lifetimes they have historically, the roughly 200 Gt CO 2 of additional emissions this century would be incompatible with keeping global warming well-below 2 °C. Thus, ambitious climate mitigation scenarios entail drastic, and perhaps un-appreciated, changes in the operating and/or retirement schedules of power infrastructure.

20 FOSSIL-FUELED POWER PLANTS↗

Comparing Parallel Plastic‐to‐X Pathways and Their Role in a Circular Economy for PET Bottles

Abstract The United States generates the most plastic waste of any country and is a top contributor to global plastic pollution. Multiple end‐of‐life strategies must be implemented to minimize environmental impacts and retain valuable plastic material, but it is challenging to compare options that generate products with different lifetimes and utilities. Herein, they present a material flow model equipped with consequential life cycle assessment, cost analysis, and a plastic circularity indicator that considers product quality and lifetime. The model is used to estimate the greenhouse gas (GHG) emissions, circularity, and cost of polyethylene terephthalate (PET) bottle mechanical downcycling to lower‐quality resin, closed‐loop glycolysis to food‐grade PET, upcycling to glass fiber‐reinforced plastic, and conversion to non‐plastic products (electricity, oil) on a United States economy‐wide basis for the year 2020. A brute force algorithm suggests that a combination of 68% glycolysis, 11% mechanical recycling, 6% upcycling, 9% landfilling, and 5% incineration can minimize the cost and GHG emissions and maximize the circularity of the current PET economy. However, uncertainty around transportation distances, materials recovery facility efficiencies, and recycling yields can result in different “optimal” pathway mixes. This flexible framework enables informed decision‐making to move toward a cost‐ and environment‐conscious circular economy for plastic.

09 BIOMASS FUELS↗

Colloidal Nanoribbons: From Infrared to Visible

Using the cation-exchange method, colloidal PbS nanoribbons are converted completely into CdS nanoribbons. This process expands the emission spectrum of the nanoribbons from infrared to visible. Here, the morphology of nanoribbons remains the same after cation exchange, but the crystal structure changes from rock salt to zincblende. CdS nanoribbons exhibit blue band-edge photoluminescence under ultraviolet-light excitation. Cathodoluminescence spectroscopy of the CdS nanoribbons shows multicolor (blue, green, and red) emissions. Further time-resolved photoluminescence spectroscopy studies show that the lifetime of the midgap states is more than 2 orders of magnitude longer than that of the band-edge states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic Behavior of Bound Interlayer Excitons in Interlayer-Doped Cs 3 Bi 2 Br 9 Vacancy-Ordered Perovskite

Interlayer doping of the vacancy-ordered 2D perovskite Cs 3 Bi 2 Br 9 (CBB) enables the formation of bound interlayer excitons (BIEs), a unique charge-transfer excited state within the layered solid. BIEs previously reported with silver (Ag + ) as an interlayer dopant exhibited bright broadband photoluminescence (PL) with prolonged lifetime at room temperature, offering potential applications in efficient white light emission, photocatalysis, and optoelectronics. However, the dynamic behavior of radiation and excited carriers remains poorly understood due to the limitations of ensemble spectroscopic measurements. Here, we investigate the temperature-dependent dynamics of Ag-doped Cs 3 Bi 2 Br 9 (Ag-CBB) using single-particle time-resolved PL spectroscopy and ultrafast transient absorption imaging. Single-particle PL measurements reveal three distinct emission regimes across temperature: (i) BIE-dominant emission at high temperatures, (ii) a mixture of radiation from BIEs and self-trapped excitons (STEs) at intermediate temperatures, and (iii) STE-dominant emission below 100 K. Rapid transient absorption mapping using Parallel Rapid Imaging with Spectroscopic Mapping (PRISM) reveals subpicosecond STE formation in pristine CBB and long-lived photoinduced absorption by BIEs, consistent with electron–hole separation and suppressed STE transfer. The spatial uniformity of these signals confirms homogeneous Ag doping across single crystals. These findings highlight the role of Ag interlayer dopants in governing the BIE dynamics.

bound interlayer exciton↗

Quantum Emitters Induced by High Pressure and UV Laser Irradiation in Multilayer GaSe

In this work, we report on defect generation in multilayer GaSe through hydrostatic pressure quenching and UV laser irradiation. The Raman line width from the UV 266 nm irradiated sample is much wider than that in pressure-quenched GaSe, corresponding to a wider defect energy distribution range in the former sample than the latter. After quenching from 11.2 GPa, three photoluminescence (PL) peaks from defect states are observed at 657, 681, and 695 nm at a low temperature of 93 K. Defect-related peaks at 649, 694, 750, and 774 nm also appear in low-temperature PL spectra after UV laser irradiation, with a nonmonotonous intensity dependence on irradiation duration. There are common features in defects produced by these two methods: the PL peaks with the lowest energy are sharp, and their PL intensities increase linearly with the excitation laser power and saturate above a certain excitation laser power. These two features are similar to those in defects for single-photon emission (SPE) in other 2D materials at even lower temperatures. Fluorescence lifetime imaging shows distinguished short (2.3 ns) and long (75.6 nm) lifetimes of the 695 nm PL line in pressure-quenched GaSe. The density functional theory predicts defect energy levels related to Se vacancy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Source Characterization of Volatile Organic Compounds at Carlsbad Caverns National Park

Carlsbad Caverns National Park (CAVE), located in southeastern New Mexico, experiences elevated ground-level ozone (O 3 ) exceeding the National Ambient Air Quality Standard (NAAQS) of 70 ppbv. It is situated adjacent to the Permian Basin, one of the largest oil and gas (O&G) producing regions in the US. In 2019, the Carlsbad Caverns Air Quality Study (CarCavAQS) was conducted to examine impacts of different sources on ozone precursors, including nitrogen oxides (NO x ) and volatile organic compounds (VOCs). Here, we use positive matrix factorization (PMF) analysis of speciated VOCs to characterize VOC sources at CAVE during the study. Seven factors were identified. Three factors composed largely of alkanes and aromatics with different lifetimes were attributed to O&G development and production activities. VOCs in these factors were typical of those emitted by O&G operations. Associated residence time analyses (RTA) indicated their contributions increased in the park during periods of transport from the Permian Basin. These O&G factors were the largest contributor to VOC reactivity with hydroxyl radicals (62%). Two PMF factors were rich in photochemically generated secondary VOCs; one factor contained species with shorter atmospheric lifetimes and one with species with longer lifetimes. RTA of the secondary factors suggested impacts of O&G emissions from regions farther upwind, such as Eagle Ford Shale and Barnett Shale formations. The last two factors were attributed to alkenes likely emitted from vehicles or other combustion sources in the Permian Basin and regional background VOCs, respectively.

54 ENVIRONMENTAL SCIENCES↗

Assessing the design of integrated methane sensing networks

Abstract While methane is the second largest contributor to global warming after carbon dioxide, it has a larger warming effect over a much shorter lifetime. Despite accelerated technological efforts to radically reduce global carbon dioxide emissions, rapid reductions in methane emissions are needed to limit near-term warming. Being primarily emitted as a byproduct from agricultural activities and energy extraction, methane is currently monitored via bottom–up (i.e. activity level) or top–down (via airborne or satellite retrievals) approaches. However, significant methane leaks remain undetected and emission rates are challenging to characterize with current monitoring frameworks. In this paper, we study the design of a layered monitoring approach that combines bottom–up and top–down approaches as an integrated sensing network. By recognizing that varying meteorological conditions and emission rates impact the efficacy of bottom–up monitoring, we develop a probabilistic approach to optimal sensor placement in its bottom–up network. Subsequently, we derive an inverse Bayesian framework to quantify the improvement that a design-optimized integrated framework has on emission-rate quantifications and their uncertainties. We find that under realistic meteorological conditions, the overall error in estimating the true emission rates is approximately 1.3 times higher, with their uncertainties being approximately 2.4 times higher, when using a randomized network over an optimized network, highlighting the importance of optimizing the design of integrated methane sensing networks. Further, we find that optimized networks can improve scenario coverage fractions by more than a factor of 2 over experimentally-studied networks, and identify a budget threshold beyond which the rate of optimized-network coverage improvement exhibits diminishing returns, suggesting that strategic sensor placement is also crucial for maximizing network efficiency.

54 ENVIRONMENTAL SCIENCES↗

Source characterization of volatile organic compounds at Carlsbad Caverns National Park

Carlsbad Caverns National Park (CAVE), located in southeastern New Mexico, experiences elevated ground-level ozone (O 3 ) exceeding the National Ambient Air Quality Standard (NAAQS) of 70 ppbv. It is situated adjacent to the Permian Basin, one of the largest oil and gas (O&G) producing regions in the US. In 2019, the Carlsbad Caverns Air Quality Study (CarCavAQS) was conducted to examine impacts of different sources on ozone precursors, including nitrogen oxides (NO x ) and volatile organic compounds (VOCs). Here, we use positive matrix factorization (PMF) analysis of speciated VOCs to characterize VOC sources at CAVE during the study. Seven factors were identified. Three factors composed largely of alkanes and aromatics with different lifetimes were attributed to O&G development and production activities. VOCs in these factors were typical of those emitted by O&G operations. Associated residence time analyses (RTA) indicated their contributions increased in the park during periods of transport from the Permian Basin. These O&G factors were the largest contributor to VOC reactivity with hydroxyl radicals (62%). Two PMF factors were rich in photochemically generated secondary VOCs; one factor contained species with shorter atmospheric lifetimes and one with species with longer lifetimes. RTA of the secondary factors suggested impacts of O&G emissions from regions farther upwind, such as Eagle Ford Shale and Barnett Shale formations. The last two factors were attributed to alkenes likely emitted from vehicles or other combustion sources in the Permian Basin and regional background VOCs, respectively. Implications: Carlsbad Caverns National Park experiences ground-level ozone exceeding the National Ambient Air Quality Standard. Volatile organic compounds are critical precursors to ozone formation. Measurements in the Park identify oil and gas production and development activities as the major contributors to volatile organic compounds. Emissions from the adjacent Permian Basin contributed to increases in primary species that enhanced local ozone formation. Observations of photochemically generated compounds indicate that ozone was also transported from shale formations and basins farther upwind. Therefore, emission reductions of volatile organic compounds from oil and gas activities are important for mitigating elevated O 3 in the region.

54 ENVIRONMENTAL SCIENCES↗

Characterization of Rare-earth Doped Thermal Barrier Coatings for Phosphor Thermometry

Thermal Barrier Coatings have been extensively used to protect and insulate the metallic components in turbine engines from extreme environments to achieve higher turbine inlet temperatures, resulting in an increase in combined engine cycle efficiency, lowering NOx emissions and fuel consumption. Additionally, as the major failure mechanisms determining lifetime are thermally activated during engine operation, uncertainty in temperature measurements affects lifetime prediction. Early detection of Thermal Barrier Coatings spallation symptoms, associated with local delamination induced temperature changes, can reduce forced engine outages. Further improvements are envisioned with the development of more reliable measurement techniques. For this purpose, Phosphor Thermometry has been considered a promising method for precision monitoring of turbine blade coatings that contain embedded phosphor dopants. In this work, a modified four-flux Kubelka-Munk model for luminescent rare-earth doped Thermal Barrier Coating configurations supported the design and the fabrication of viable sensing coatings for potential industrial implementation. Phosphor Thermometry instrumentation was developed with the objective of expanding capabilities of the technique, using a synchronized acquisition method on sensing coatings. Experiments on an innovative Erbium-Europium co-doped Yttria-Stabilized Zirconia coating have demonstrated the effectiveness of this advanced Phosphor Thermometry instrument with enhanced sensitivity and extended temperature range. Delamination progression monitoring was achieved for the first time using a Thermal Barrier Coating configuration subjected to indentation that includes a thin luminescent layer deposited on the surface and associating the multi-layer configuration with a predictive model that evaluates the advancement of the degradation of the coatings. To further ensure the integrity of the phosphor doped coatings, synchrotron X-ray diffraction was performed to characterize the specific residual strains and thermal expansion of the materials, determining mechanical robustness and compatibility with state-of-the-art Thermal Barrier Coatings. The outcomes of this work pave the way for in-situ temperature measurements on phosphor-doped turbine blade coatings with increased performance and accuracy.

Fouliard, Quentin↗

Challenging Common Assumptions of Thick-Wall Chamber Dynamics in Inertial Fusion Systems using MOOSE

As an increasing number of companies look toward commercial Inertial Fusion Energy (IFE) designs, there is a pressing need to understand the physics of thick-wall chamber gas dynamics. The thick liquid wall approach implements a renewable wall to mitigate the fusion target emissions, thereby reducing the radiation damage rate and significantly extending the lifetime of chamber structures, leading to increased plant availability and reduced waste streams in comparison to dry wall chamber designs. It is necessary, however, to assess the critical performance and safety aspects of these systems. For example, it is crucial to predict (1) where the mass ablated from the liquid walls will vent, which determines the placement of condensing surfaces; (2) debris propagation up the beam lines, which provides essential information for design and protection requirements; (3) peak pressures and impulse on chamber walls, which affect chamber structural design; and (4) momentum transfer to the liquid jets, which constrains the shape and positioning of the jets. In turn, the chamber design and its liquid walls affect shielding requirements, material activation, and tritium fuel cycle. Currently available simulation tools, however, are unable to accurately capture key thick-wall chamber dynamics. Significant assumptions are often made to simplify the system and reduce computational cost and modeling capability needs, but the impact of these assumptions on simulation predictions has not been evaluated. For example, no three-dimensional simulations can be found in the open literature to evaluate gas venting and momentum transfer to the jets with simulations using two-dimensional domains to represent complex three-dimensional geometries. Moreover, limited studies have been dedicated to jet breakup due to both turbulence and neutron heating, and no studies have been found that evaluate how jet breakup can impact shock-jet interaction. Furthermore, effects of radiative heat transfer have rarely been included for the hydrodynamic phase of shock propagation, and integration of proper equations of state in shock dynamics codes has been mostly exploratory. In this study, we use the flexible, high-fidelity Multiphysics Object-Oriented Simulation Environment (MOOSE) to model these complex phenomena and inform design and safety studies. Capabilities to model thick-wall chamber gas dynamics are being developed, and the impact of the assumptions listed above (i.e., two-dimensional vs three-dimensional, absence of jet breakout, no radiative heat transfer, and ideal gas behavior) are being quantified.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Challenging Common Assumptions of Thick-Wall Chamber Dynamics in Inertial Fusion Systems Using MOOSE-based Multiphysics Simulations

As an increasing number of companies look toward commercial Inertial Fusion Energy (IFE) designs, there is a pressing need to understand the physics of thick-wall chamber gas dynamics. The thick liquid wall approach implements a renewable wall to mitigate the fusion target emissions, thereby reducing the radiation damage rate and significantly extending the lifetime of chamber structures, leading to increased plant availability and reduced waste streams in comparison to dry wall chamber designs. It is necessary, however, to assess the critical performance and safety aspects of these systems. For example, it is crucial to predict (1) where the mass ablated from the liquid walls will vent, which determines the placement of condensing surfaces; (2) debris propagation up the beam lines, which provides essential information for design and protection requirements; (3) peak pressures and impulse on chamber walls, which affect chamber structural design; and (4) momentum transfer to the liquid jets, which constrains the shape and positioning of the jets. In turn, the chamber design and its liquid walls affect shielding requirements, material activation, and tritium fuel cycle. Currently available simulation tools, however, are unable to accurately capture key thick-wall chamber dynamics. Significant assumptions are often made to simplify the system and reduce computational cost and modeling capability needs, but the impact of these assumptions on simulation predictions has not been evaluated. For example, no three-dimensional simulations can be found in the open literature to evaluate gas venting and momentum transfer to the jets with simulations using two-dimensional domains to represent complex three-dimensional geometries. Moreover, limited studies have been dedicated to jet breakup due to both turbulence and neutron heating, and no studies have been found that evaluate how jet breakup can impact shock-jet interaction. Furthermore, effects of radiative heat transfer have rarely been included for the hydrodynamic phase of shock propagation, and integration of proper equations of state in shock dynamics codes has been mostly exploratory. In this study, we use the flexible, high-fidelity Multiphysics Object-Oriented Simulation Environment (MOOSE) to model these complex phenomena and inform design and safety studies. Capabilities to model thick-wall chamber gas dynamics are being developed, and the impact of the assumptions listed above (i.e., two-dimensional vs three-dimensional, absence of jet breakout, no radiative heat transfer, and ideal gas behavior) are being quantified.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Why Increased CdSeTe Charge Carrier Lifetimes and Radiative Efficiencies did not Result in Voltage Boost for CdTe Solar Cells

After a focused effort over the last decade, order-of-magnitude improvements in doping and electro-optical characteristics (radiative efficiency, carrier lifetime, and passivation) have been reported for polycrystalline CdSeTe solar cells. Surprisingly, this did not result in higher solar cell voltages regardless of device contacting layers, absorber grading profiles, and other changes in device architecture. From detailed evaluation of radiative emission and carrier dynamics in CdSeTe heterostructures and devices, it is shown that the complexity introduced to the absorber to achieve lifetime and passivation metrics resulted in charge carrier trapping, which now negatively affects CdSeTe absorbers.

CdTe↗

Naphthodithiophene‐Fused Porphyrins: Synthesis, Characterization, and Impact of Extended Conjugation on Aromaticity

The fusion of tetrapyrroles with aromatic heterocycles constitutes a useful tool for manipulating their opto-electronic properties. In this work, the synthesis of naphthodithiophene-fused porphyrins was achieved through a Heck reaction-based cascade of steps followed by the Scholl reaction. The naphthodithiophene-fused porphyrins display a unique set of optical and electronic properties. Fusion of the naphtho[2,1-b:3,4-b’]dithiophene to porphyrin (F2VTP) leads to a ~20% increase in the fluorescence lifetime, which is accompanied, unexpectedly, by a more than two-fold drop in the emission quantum yield (ϕ=0.018). In contrast, fusion of the isomeric naphtho[1,2-b:4,3-b’]dithiophene to porphyrin (F3VPT) results in a ~1.5-fold increase in the fluorescence quantum yield (ϕ=0.13) with a concomitant ~30 % increase in the fluorescence lifetime. This behavior suggests that fusion of the porphyrin with the naphthodithiopheno-system mainly affects the radiative rate constant in the Q-state deactivation pathway, where the effects of the isomeric naphtho[2,1-b:3,4-b’]dithiophene- versus naphtho[1,2-b:4,3-b’]dithiophene-fusion are essentially the opposite. Interestingly, nucleus-independent chemical shifts analysis revealed a considerable difference between the aromaticities of these two isomeric systems. Furthermore, our results demonstrate that subtle structural differences in the fused components of the porphyrin can be reflected in rather significant differences between the photophysical properties of the resulting systems.

Chemistry↗

Global Methane Budget 2000–2020

Abstract. Understanding and quantifying the global methane (CH4) budget is important for assessing realistic pathways to mitigate climate change. CH4 is the second most important human-influenced greenhouse gas in terms of climate forcing after carbon dioxide (CO2), and both emissions and atmospheric concentrations of CH4 have continued to increase since 2007 after a temporary pause. The relative importance of CH4 emissions compared to those of CO2 for temperature change is related to its shorter atmospheric lifetime, stronger radiative effect, and acceleration in atmospheric growth rate over the past decade, the causes of which are still debated. Two major challenges in quantifying the factors responsible for the observed atmospheric growth rate arise from diverse, geographically overlapping CH4 sources and from the uncertain magnitude and temporal change in the destruction of CH4 by short-lived and highly variable hydroxyl radicals (OH). To address these challenges, we have established a consortium of multidisciplinary scientists under the umbrella of the Global Carbon Project to improve, synthesise, and update the global CH4 budget regularly and to stimulate new research on the methane cycle. Following Saunois et al. (2016, 2020), we present here the third version of the living review paper dedicated to the decadal CH4 budget, integrating results of top-down CH4 emission estimates (based on in situ and Greenhouse Gases Observing SATellite (GOSAT) atmospheric observations and an ensemble of atmospheric inverse-model results) and bottom-up estimates (based on process-based models for estimating land surface emissions and atmospheric chemistry, inventories of anthropogenic emissions, and data-driven extrapolations). We present a budget for the most recent 2010–2019 calendar decade (the latest period for which full data sets are available), for the previous decade of 2000–2009 and for the year 2020. The revision of the bottom-up budget in this 2025 edition benefits from important progress in estimating inland freshwater emissions, with better counting of emissions from lakes and ponds, reservoirs, and streams and rivers. This budget also reduces double counting across freshwater and wetland emissions and, for the first time, includes an estimate of the potential double counting that may exist (average of 23 Tg CH4 yr−1). Bottom-up approaches show that the combined wetland and inland freshwater emissions average 248 [159–369] Tg CH4 yr−1 for the 2010–2019 decade. Natural fluxes are perturbed by human activities through climate, eutrophication, and land use. In this budget, we also estimate, for the first time, this anthropogenic component contributing to wetland and inland freshwater emissions. Newly available gridded products also allowed us to derive an almost complete latitudinal and regional budget based on bottom-up approaches. For the 2010–2019 decade, global CH4 emissions are estimated by atmospheric inversions (top-down) to be 575 Tg CH4 yr−1 (range 553–586, corresponding to the minimum and maximum estimates of the model ensemble). Of this amount, 369 Tg CH4 yr−1 or ∼ 65 % is attributed to direct anthropogenic sources in the fossil, agriculture, and waste and anthropogenic biomass burning (range 350–391 Tg CH4 yr−1 or 63 %–68 %). For the 2000–2009 period, the atmospheric inversions give a slightly lower total emission than for 2010–2019, by 32 Tg CH4 yr−1 (range 9–40). The 2020 emission rate is the highest of the period and reaches 608 Tg CH4 yr−1 (range 581–627), which is 12 % higher than the average emissions in the 2000s. Since 2012, global direct anthropogenic CH4 emission trends have been tracking scenarios that assume no or minimal climate mitigation policies proposed by the Intergovernmental Panel on Climate Change (shared socio-economic pathways SSP5 and SSP3). Bottom-up methods suggest 16 % (94 Tg CH4 yr−1) larger global emissions (669 Tg CH4 yr−1, range 512–849) than top-down inversion methods for the 2010–2019 period. The discrepancy between the bottom-up and the top-down budgets has been greatly reduced compared to the previous differences (167 and 156 Tg CH4 yr−1 in Saunois et al. (2016, 2020) respectively), and for the first time uncertainties in bottom-up and top-down budgets overlap. Although differences have been reduced between inversions and bottom-up, the most important source of uncertainty in the global CH4 budget is still attributable to natural emissions, especially those from wetlands and inland freshwaters. The tropospheric loss of methane, as the main contributor to methane lifetime, has been estimated at 563 [510–663] Tg CH4 yr−1 based on chemistry–climate models. These values are slightly larger than for 2000–2009 due to the impact of the rise in atmospheric methane and remaining large uncertainty (∼ 25 %). The total sink of CH4 is estimated at 633 [507–796] Tg CH4 yr−1 by the bottom-up approaches and at 554 [550–567] Tg CH4 yr−1 by top-down approaches. However, most of the top-down models use the same OH distribution, which introduces less uncertainty to the global budget than is likely justified. For 2010–2019, agriculture and waste contributed an estimated 228 [213–242] Tg CH4 yr−1 in the top-down budget and 211 [195–231] Tg CH4 yr−1 in the bottom-up budget. Fossil fuel emissions contributed 115 [100–124] Tg CH4 yr−1 in the top-down budget and 120 [117–125] Tg CH4 yr−1 in the bottom-up budget. Biomass and biofuel burning contributed 27 [26–27] Tg CH4 yr−1 in the top-down budget and 28 [21–39] Tg CH4 yr−1 in the bottom-up budget. We identify five major priorities for improving the CH4 budget: (i) producing a global, high-resolution map of water-saturated soils and inundated areas emitting CH4 based on a robust classification of different types of emitting ecosystems; (ii) further development of process-based models for inland-water emissions; (iii) intensification of CH4 observations at local (e.g. FLUXNET-CH4 measurements, urban-scale monitoring, satellite imagery with pointing capabilities) to regional scales (surface networks and global remote sensing measurements from satellites) to constrain both bottom-up models and atmospheric inversions; (iv) improvements of transport models and the representation of photochemical sinks in top-down inversions; and (v) integration of 3D variational inversion systems using isotopic and/or co-emitted species such as ethane as well as information in the bottom-up inventories on anthropogenic super-emitters detected by remote sensing (mainly oil and gas sector but also coal, agriculture, and landfills) to improve source partitioning. The data presented here can be downloaded from https://doi.org/10.18160/GKQ9-2RHT (Martinez et al., 2024).

54 ENVIRONMENTAL SCIENCES↗

Investigation of Sub‐Bandgap Emission and Unexpected n‐Type Behavior in Undoped Polycrystalline CdSe x Te 1‐x

Abstract Se alloying has enabled significantly higher carrier lifetimes and photocurrents in CdTe solar cells, but these benefits can be highly dependent on CdSe x Te 1‐x processing. This work evaluates the optoelectronic, chemical, and electronic properties of thick (3 µm) undoped CdSe x Te 1‐x of uniform composition and varied processing conditions (CdSe x Te 1‐x evaporation rate, CdCl 2 anneal, Se content) chosen to reflect various standard device processing conditions. Sub‐bandgap defect emission is observed, which increased as Se content increased and with “GrV‐optimized CdCl 2 ” (i.e., CdCl 2 anneal conditions used for group‐V‐doped devices). Low carrier lifetime is found for GrV‐optimized CdCl 2 , slow CdSe x Te 1‐x deposition, and low‐Se films. Interestingly, all films (including CdTe control) exhibited n‐type behavior, where electron density increased with Se up to an estimated ≈10 17 cm −3 . This behavior appears to originate during the CdCl 2 anneal, possibly from Se diffusion leading to anion vacancy (e.g., V Se , V Te ) and Cl Te generation.

14 SOLAR ENERGY↗

Radiative lifetime-encoded unicolour security tags using perovskite nanocrystals

Traditional fluorescence-based tags, used for anticounterfeiting, rely on primitive pattern matching and visual identification; additional covert security features such as fluorescent lifetime or pattern masking are advantageous if fraud is to be deterred. Herein, we present an electrohydrodynamically printed unicolour multi-fluorescent-lifetime security tag system composed of lifetime-tunable lead-halide perovskite nanocrystals that can be deciphered with both existing time-correlated single-photon counting fluorescence-lifetime imaging microscopy and a novel time-of-flight prototype. We find that unicolour or matching emission wavelength materials can be prepared through cation-engineering with the partial substitution of formamidinium for ethylenediammonium to generate “hollow” formamidinium lead bromide perovskite nanocrystals; these materials can be successfully printed into fluorescence-lifetime-encoded-quick-read tags that are protected from conventional readers. Furthermore, we also demonstrate that a portable, cost-effective time-of-flight fluorescence-lifetime imaging prototype can also decipher these codes. A single comprehensive approach combining these innovations may be eventually deployed to protect both producers and consumers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗