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Effect of pattern transfer process on roughness of block copolymer patterns from directed self-assembly
Block copolymer-directed self-assembly (DSA) remains promising for improving pattern quality and reducing the stochastic variations that challenge high numerical aperture extreme ultraviolet lithography. Equally critical is refining pattern transfer methods for accurately transferring the rectified DSA features to the underlying substrate. We compare two atomic layer deposition (ALD)-based techniques: sequential infiltration synthesis (SIS) and dry liftoff, applied to polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) DSA patterns. Both methods utilize aluminum oxide hard masks, with one synthesized through infiltration into the PMMA domains and the other through conformal ALD coating. High-resolution scanning electron micrographs were analyzed to measure line edge, width, and placement roughness for both the line (PMMA) and space (PS) features. Although both methods yielded similar overall 3σ rms roughness, they differed significantly in the frequency-dependent power spectral density (PSD) profiles. SIS reduced line placement roughness at length scales associated with the polymer pitch, but increased space width roughness at low frequencies, whereas dry liftoff mimicked the frequency content of the original guiding pattern. This study underscores the importance of PSD evaluation in selecting optimal pattern transfer strategies for specific applications.
Carbon Capture Pilot at Dry Fork Power Station (Final Technical Report)
The objective of this project was to design, seek necessary approvals, build and operate a large-scale pilot sorbent-based post combustion carbon capture system (CCS) at a coal fired power generation facility. TDA’s CCS uses a highly stable, low-cost, high-capacity physical adsorbent to effectively remove CO 2 via a combination vacuum and concentration swing adsorption (VCSA) process. The CCS is integrated with the power plant flue gas exhaust, which is rich in CO 2 (~13% vol. CO 2 ) and removes more than 90% of the plant’s overall carbon emissions.
Above-ground net primary productivity in regenerating seasonally dry tropical forest: Contributions of rainfall, forest age and soil
Identifying factors controlling forest productivity is critical to understanding forest-climate change feedbacks, modelling vegetation dynamics and carbon finance schemes. However, little research has focused on productivity in regenerating tropical forests which are expanding in their fraction of global area have an order of magnitude larger carbon uptake rates relative to older forest. Here We examined above-ground net primary productivity (ANPP) and its components (wood production and litterfall) over 10 years in forest plots that vary in successional age, soil characteristics and species composition using band dendrometers and litterfall traps in regenerating seasonally dry tropical forests in northwestern Costa Rica. We show that the components of ANPP are differentially driven by age and annual rainfall and that local soil variation is important. Total ANPP was explained by a combination of age, annual rainfall and soil variation. Wood production comprised 35% of ANPP on average across sites and years, and was explained by annual rainfall but not forest age. Conversely, litterfall increased with forest age and soil fertility yet was not affected by annual rainfall. In this region, edaphic variability is highly correlated with plant community composition. Thus, variation in ecosystem processes explained by soil may also be partially explained by species composition. These results suggest that future changes in annual rainfall can alter the secondary forest carbon sink, but this effect will be buffered by the litterfall flux which varies little among years. In determining the long-term strength of the secondary forest carbon sink, both rainfall and forest age will be critical variables to track. We also conclude that detailed understanding of local site variation in soils and plant community may be required to accurately predict the impact of changing rainfall on forest carbon uptake. Synthesis. We show that in seasonally dry tropical forest, annual rainfall has a positive relationship with the growth of above-ground woody tissues of trees and that droughts lead to significant reductions in above-ground productivity. These results provide evidence for climate change—carbon cycle feedbacks in the seasonal tropics and highlight the value of longitudinal data on forest regeneration.
Phase segregation mechanisms of small molecule-polymer blends unraveled by varying polymer chain architecture
As phase separation between the small-molecule semiconductor and the polymer binder is the key enabler of blend-based organic field-effect transistors (OFETs) fabricated by low-cost solution processing, it is crucial to understand the underlying phase separation mechanisms that determine the phase morphology, which significantly impacts device performance. Beyond the parameter space investigated in previous work, here we investigate the formation of blends by varying the branch architecture of the polymer binder and by shortening the solvent dry time using ultrasonic spray casting. The phase morphologies of the resulting blend films have been thoroughly characterized with a variety of techniques in three dimensions over multiple length scales, including AFM, energy-filtered transmission electron microscope, and neutron reflectivity, and have been correlated with electrical transport performance. From the results, we have inferred that the phase morphology is kinetically determined, limited by the inherent slow movement of polymer macromolecules. The kinetic picture, supported by molecular dynamics modeling, not only consistently explains our observations but also resolves inconsistencies in previous works. The achieved mechanistic understanding will guide further optimization of blend-based organic electronics, such as OFETs and organic photovoltaics.
Moisture sources for precipitation variability over the Arabian Peninsula
Abstract We apply the Lagrangian-based moisture back trajectory method to two reanalysis datasets to determine the moisture sources for wet season precipitation over the Arabian Peninsula, defined as land on the Asian continent to the south of the Turkish border and west of Iran. To accomplish this, we make use of the evaporative source region between 65°W–120°E and 30°S–60°N, which is divided into twelve sub-regions. Our comparison of reanalyses and multiple observations allows us to validate datasets and highlight broad-scale similarities in characteristics, notwithstanding some inconsistencies in the southwest AP. The results indicate north-to-south spatiotemporal heterogeneity in the characteristics of dominant moisture sources. In the north, moisture for precipitation is mainly sourced from midlatitude land and water bodies, such as the Mediterranean and Caspian Seas. Areas further south are dependent on moisture transport from the Western Indian Ocean and parts of the African continent. The El Niño-Southern Oscillation (ENSO) exhibits an overall positive but sub-seasonally varying influence on the precipitation variability over the region, with noticeable moisture anomalies from all major source regions. A significant drying trend exists over parts of the Peninsula, which both reanalyses partially attribute to anomalies in the moisture advection from the Congo Basin and South Atlantic Ocean. However, considerable uncertainty in evaporation trends over the terrestrial evaporative sources in observations warrants additional modeling studies to further our understanding of key processes contributing to the negative trends.
Falling-film thermosyphons: Application to water harvesting from humid gas streams
Water harvesting from humid gas streams is central to fresh-water production, desalination, and particulate removal from combustion gas streams. Two-phase thermosyphons are well suited for these applications due to their very low thermal resistance, but have several operating limits at the high heat flows required for such applications. This work introduces the falling-film thermosyphon for large-scale condensation applications. Working fluid is pumped to the top of the evaporator to provide the evaporating liquid film on the inner tube wall, rather than by vapor condensation. The flooding, dry-out and pool-boiling limits are eliminated, resulting in significantly higher maximum heat fluxes for the same physical evaporator size. Furthermore, the condenser no longer needs to be located vertically above the evaporator, which allows for a standard steam condenser to be used. A model for the condensation process in humid air was developed that estimates the fluid and heat transfer and is confirmed experimentally. Further benefits include the use of a high-thermal-conductivity polymer material for the evaporator section to minimize corrosion, and the ability to impose a temperature boundary condition on the evaporator, which is made possible due to the elimination of a liquid pool.
Evaluating Autoxidation Radical Scavengers and Additives to Enhance Aminopolymer Sorbent Stability
Solid amine sorbents have shown promise in the removal of ultradilute CO 2 from the atmosphere. Despite being a promising candidate material type for this application, these sorbents are prone to degradation during long-term exposure to environmental components such as CO 2 , O 2 , and H 2 O, with amine oxidation being a particularly challenging problem. In this study, we investigate the potency of different radical scavengers and additives in mitigating the degradation of a model poly- (ethylenimine) (PEI)/Al 2 O 3 sorbent under direct air capture (DAC)-relevant conditions. The results reveal that a 4,4′-bis(α,α- dimethylbenzyl)diphenylamine (BDDPA)-incorporated PEI/Al 2 O 3 sorbent showed the most resistance toward oxidative degradation at varying exposure times and BDDPA loadings under CO 2 -free air (21% O 2 /balance N 2 ) at 120 °C. Interestingly, under humid (∼43% relative humidity (RH) at 26 °C) and dry 0.04% CO 2 -air, the BDDPA/PEI/Al 2 O 3 sorbent showed enhanced sorbent stability both at 70 and 120 °C after 4.5 h of exposure. Under humid CO 2 -free air, at 120 °C, the antioxidant performance slightly declined (in comparison to the dry CO 2 -free air condition) but displayed a much higher stability than the pristine sorbent. Overall, the ability of BDDPA to inhibit sorbent degradation under dry and humid, CO 2 -free and CO 2 -containing (0.04%) air at intermediate (70 °C) and elevated (120 °C) temperatures is promising in prolonging sorbent stability and underscores the importance of performing accelerated oxidation studies in the presence of all species that are expected to be present in DAC processes to identify suitable stabilization treatments for sorbent materials.
Biogeochemical and community ecology responses to the wetting of non-perennial streams
Transitions between dry and wet hydrologic states are the defining characteristic of non-perennial rivers and streams, which constitute the majority of the global river network. Although past work has focused on stream drying characteristics, there has been less focus on how hydrology, ecology and biogeochemistry respond and interact during stream wetting. Wetting mechanisms are highly variable and can range from dramatic floods and debris flows to gradual saturation by upwelling groundwater. This variation in wetting affects ecological and biogeochemical functions, including nutrient processing, sediment transport and the assembly of biotic communities. Here, in this work, we synthesize evidence describing the hydrological mechanisms underpinning different types of wetting regimes, the associated biogeochemical and organismal responses, and the potential scientific and management implications for downstream ecosystems. This combined multidisciplinary understanding of wetting dynamics in non-perennial streams will be key to predicting and managing for the effects of climate change on non-perennial ecosystems.
Constraining long‐term model predictions for woody growth using tropical tree rings
The strength and persistence of the tropical carbon sink hinges on the long-term responses of woody growth to climatic variations and increasing CO 2 . However, the sensitivity of tropical woody growth to these environmental changes is poorly understood, leading to large uncertainties in growth predictions. Here, we used tree ring records from a Southeast Asian tropical forest to constrain ED2.2-hydro, a terrestrial biosphere model with explicit vegetation demography. Specifically, we assessed individual-level woody growth responses to historical climate variability and increases in atmospheric CO 2 (C a ). When forced with historical C a , ED2.2-hydro reproduced the magnitude of increases in intercellular CO 2 concentration (a major determinant of photosynthesis) estimated from tree ring carbon isotope records. In contrast, simulated growth trends were considerably larger than those obtained from tree rings, suggesting that woody biomass production efficiency (WBPE = woody biomass production:gross primary productivity) was overestimated by the model. The estimated WBPE decline under increasing C a based on model-data discrepancy was comparable to or stronger than (depending on tree species and size) the observed WBPE changes from a multi-year mature-forest CO 2 fertilization experiment. In addition, we found that ED2.2-hydro generally overestimated climatic sensitivity of woody growth, especially for late-successional plant functional types. The model-data discrepancy in growth sensitivity to climate was likely caused by underestimating WBPE in hot and dry years due to commonly used model assumptions on carbon use efficiency and allocation. To our knowledge, this is the first study to constrain model predictions of individual tree-level growth sensitivity to C a and climate against tropical tree-ring data. Our results suggest that improving model processes related to WBPE is crucial to obtain better predictions of tropical forest responses to droughts and increasing C a . Finally, more accurate parameterization of WBPE will likely reduce the stimulation of woody growth by C a rise predicted by biosphere models.
High-performance computing in water resources hydrodynamics
In this work, we present a vision of future water resources hydrodynamics codes that can fully utilize the strengths of modern high-performance computing. The advances to computing power, formerly driven by the improvement of central processing unit processors, now focus on parallel computing and, in particular, the use of graphics processing units (GPUs). However, this shift to a parallel framework requires refactoring the code to make efficient use of the data as well as changing even the nature of the algorithm that solves the system of equations. These concepts along with other features such as the precision for the computations, dry regions management, and input/output data are analyzed in this paper. A 2D multi-GPU flood code applied to a large-scale test case is used to corroborate our statements and ascertain the new challenges for the next-generation parallel water resources codes.
SAIL Supermicron Bioaerosol (SSB) Field Campaign Report
The Surface Atmosphere Integrated Field Laboratory (SAIL) Supermicron Bioaerosol (SSB) study was designed to complement the larger Atmospheric Radiation Measurement (ARM) SAIL science goals to understand aerosol processes and aerosol-cloud interactions in the Colorado River’s East River Watershed Basin. Supermicron aerosol, particles larger than one micron in diameter, and bioaerosols, primary particles containing biological material, are important for understanding atmospheric processes and sources within high mountainous terrain. For example, they can interact with clouds and the water cycle such as by serving as nuclei for cloud droplets and ice crystals that can eventually result in precipitation events. These particles can also be recycled back to the surface via wet and dry deposition, where they can alter plant and microbial growth and/or be reemitted again, forming a positive feedback loop within the Earth system known as bioprecipitation.
Exploration of reduced graphene oxide microparticles as electrocatalytic materials in vanadium redox flow batteries
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Energy-valley-dependent charge transfer in few-layer transition metal dichalcogenide heterostructures
The effect of the energy valley on interlayer charge transfer in transition metal dichalcogenide (TMD) heterostructures is studied by transient absorption spectroscopy and density functional theory. First-principles calculations confirm that the Λ min valley in the conduction band of few-layer WSe 2 evolves from above its K valley in the monolayer (1L) to below it in 4L. Heterostructure samples of nL–WSe 2 /1L–MoS 2 , where n = 1,2,3, and 4, are obtained by mechanical exfoliation and dry transfer. Photoluminescence spectroscopy reveals a thickness-dependent WSe 2 band structure and efficient interlayer charge transfer. Transient absorption measurements show that the electron transfer time from the Λ min valley of 4L WSe 2 to the K valley of MoS 2 is on the order of 30 ps. This process is much slower than the K-K charge transfer in 1L/1L TMD heterostructures. Furthermore, the momentum-indirect interlayer excitons formed after charge transfer have lifetimes >1 ns.
Warm air intrusions reaching the MOSAiC expedition in April 2020—The YOPP targeted observing period (TOP)
In the spring period of the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition, an initiative was in place to increase the radiosounding frequency during warm air intrusions in the Atlantic Arctic sector. Two episodes with increased surface temperatures were captured during April 12–22, 2020, during a targeted observing period (TOP). The large-scale circulation efficiently guided the pulses of warm air into the Arctic and the observed surface temperature increased from -30°C to near melting conditions marking the transition to spring, as the temperatures did not return to values below -20°C. Back-trajectory analysis identifies 3 pathways for the transport. For the first temperature maximum, the circulation guided the airmass over the Atlantic to the northern Norwegian coast and then to the MOSAiC site. The second pathway was from the south, and it passed over the Greenland ice sheet and arrived at the observational site as a warm but dry airmass due to precipitation on the windward side. The third pathway was along the Greenland coast and the arriving airmass was both warm and moist. The back trajectories originating from pressure levels between 700 and 900 hPa line up vertically, which is somewhat surprising in this dynamically active environment. The processes acting along the trajectory originating from 800 hPa at the MOSAIC site are analyzed. Vertical profiles and surface energy exchange are presented to depict the airmass transformation based on ERA5 reanalysis fields. The TOP could be used for model evaluation and Lagrangian model studies to improve the representation of the small-scale physical processes that are important for airmass transformation. A comparison between MOSAiC observations and ERA5 reanalysis demonstrates challenges in the representation of small-scale processes, such as turbulence and the contributions to various terms of the surface energy budget, that are often misrepresented in numerical weather prediction and climate models.
Precision Plant Biomass Characterization in Agriculture: Harnessing Machine Learning and Hyperspectral Imaging [Slides]
Efficient Biomass Separation Object detection of anatomical parts (Cob, Stalk, Husk) in IR images enables precise separation, improving preprocessing (e.g., drying, grinding) for biofuel production. Detailed Biomass Characterization with Hyperspectral Data Hyperspectral imaging captures spectral signatures of biomass, allowing for the identification of specific traits like moisture content, lignin levels, and nutrient composition, leading to optimized treatments for each biomass part. Enhanced Feedstock Quality By leveraging hyperspectral data, feedstock can be processed based on its chemical composition, improving conversion efficiency and biofuel yield. Automation for Large-Scale Operations Automated object detection and hyperspectral data analysis reduce manual labor, ensuring accurate sorting and faster processing, making large-scale biofuel production more efficient. Maximized Biomass Utilization Accurate identification of biomass properties minimizes waste and ensures that each part is processed according to its highest biofuel potential.
Two-dimensional heteronuclear single quantum coherence (HSQC) NMR spectra of lignin isolated from Populus trichocarpa residues after CELF pretreatment and CBP fermentation
Here we present a curated dataset of a series of two-dimensional heteronuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR) spectra of lignin isolated from a woody energy crop (Populus trichocarpa) residues after co-solvent enhanced lignocellulosic fractionation (CELF) pretreatment and consolidated bioprocessing (CBP) process. The natural poplar variant GW-9947 from the Center for Bioenergy Innovation (CBI) was used. The poplar was knife milled and passed through a 1 mm sieve. The CELF pretreatment was performed in a Parr autoclave reactor with 7.5 wt % solids loading, 0.5 wt% H2SO4 as catalyst at 150°C with 15, 25 and 30 minutes, respectively. Tetrahydrofuran was added in a 1:1 mass ratio with water as the pretreatment solvent. The residues from CELF pretreatment were then subjected to CBP using the bacterium C. thermocellum DSM 1313. CBP fermentations were performed at 60 °C in a shaker at 50 grams/L solids loadings. Lignin was isolated from the pretreated samples after ball-milling in a porcelain jar with ceramic balls via Retsch PM 200 at 580 rpm for 2.5 h followed by enzymatic hydrolysis in acetate buffer (pH 4.8, 50 °C) for 48 h. The lignin samples were characterized using 13C–1H HSQC experiments which were performed in a Bruker Avance III HD 500 MHz NMR spectrometer operating at a frequency of 125.12 MHz for the 13C nucleus. A standard Bruker pulse sequence was used on a Prodigy platform cryoprobe. The dry lignin samples were dissolved in deuterated dimethylsulfoxide for HSQC experiments. The spectra were acquired under the following acquisition conditions: 210 ppm spectral width in F1 (13C) dimension with 256 data points and 11 ppm spectral width in F2 (1H) dimension with 1024 data points, a 90° pulse, a one bond C–H coupling constant of 145 Hz, a 1.0 s pulse delay, and 64 scans. All the data was processed using the TopSpin 3.6 software (Bruker BioSpin). The NMR spectra provides structural characteristics information about lignin remaining in solids after CELF (150 °C with 15, 25 and 30 minutes) process and C. thermocellum CBP.
Air oxidation of yttrium hydride as a high temperature moderator for thermal neutron spectrum fission reactors
Yttrium hydride (YH x ) is an attractive moderator material for thermal neutron spectrum fission reactors requiring a small reactor core volume and has been selected as the neutron moderator for the Transformational Challenge Reactor (TCR), an advanced gas-cooled microreactor. Before YH x can be used in this application, it is important to understand the material response to off-normal conditions. In the present study, 550–650 °C isothermal dry air oxidation was performed to simulate a depressurized loss of force circulation (DLOFC) event. The oxidation was performed using thermogravimetric analysis (TGA) on bulk crack-free YHx coupons. Oxidation studies were also performed on Y coupons to elucidate the impact of H on oxidation. Both the chemistry and distribution of processing impurities were found to strongly affect oxidization behavior on a batch-to-batch basis. Regardless of batch, YHx oxidized at a significantly lower rate than Y at all temperatures, and the lower rate was directly correlated with increased hydride content. Metallic Y exhibited complex exponential kinetics, whereas YH x also exhibited complex kinetics but gained considerably less mass. According to literature reports on protonic and native-ion conductivities of Y 2 O 3 and mass spectrometry analysis of gaseous reaction products formed during the oxidation of YH x , a mechanism for the reduced oxidation rate of yttrium hydride is suggested.