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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Challenges in Kinetic modeling of ammonia pyrolysis

Ammonia pyrolysis reactions have implications for its ignition and oxidation in engines and gas turbines. In the present work, the chemistry of ammonia pyrolysis is investigated by kinetic modeling and theory. Rate constants for key reactions are carefully evaluated based on available experimental and theoretical results. The high pressure limit k1,∞ for NH 2 + H (+M) ⇄ NH 3 (+M) (R1) is calculated to be essentially the collision frequency, indicating that dissociation of ammonia in combustion processes will be at or close to the low pressure limit even at engine and gas turbine conditions. The chemical kinetic model is validated against reported shock tube measurements of NH 3 , NH 2 , and NH in ammonia pyrolysis. Predictions are in good agreement with observations for dilute conditions (≤ 0.5% NH 3 ), but the model appears to underpredict the NH 3 consumption rate at longer times in less dilute mixtures. At short reaction times, thermal dissociation of NH3, together with the NH 3 + H reaction, controls conversion. At longer times, secondary reactions involving NH 2 and NH become important due to their impact on the radical pool. Predictions become sensitive to formation and consumption of diazene (tHNNH and cHNNH). Several of the key steps in the ammonia pyrolysis mechanism are radical-radical reactions that are difficult to measure accurately and challenging to calculate theoretically, and a more comprehensive experimental characterization is desirable to support further model development.

10 SYNTHETIC FUELS↗
DOE OSTI2022

Property-structure-process relationships in dissimilar material repair with directed energy deposition: Repairing gray cast iron using stainless steel 316L

Directed energy deposition (DED) based remanufacturing leverages the flexibility of additive manufacturing to add value to broken or worn components. DED offers the ability to repair cast iron, a material difficult to repair with traditional welding techniques. Despite this, development of appropriate DED process conditions for bimetallic cast iron structures lags low- and medium-carbon steel repair. Thermal stresses and porosity generated by high-temperature deposition on cast iron often lower mechanical properties and hinder the qualification process. In this report scanning speed, powder mass flow rate, and stepover width are studied in multiple-track structures deposited on gray cast iron. Dilution and residual stresses are found to be highly dependent on the selected process parameters. Samples with a higher volumetric energy input, e.g., slower scanning speeds and higher powder feed rates, showed improved density and lower residual stresses but suffered lower dilution into the substrate. The presented conditions further the development of additive manufacturing technologies for automotive repair.

42 ENGINEERING↗
NASA NTRS1972

Study of mechanism which causes film formation on mercury surfaces

The mechanism by which small quantities of dissolved tin, sodium, and lithium lower the rate of evaporation of mercury in vacuum is determined. An apparatus was built in which dilute amalgams could be prepared and studied in an oxygen-free environment before being exposed to oxygen under controlled conditions. The apparatus was able to maintain a pressure of less than 1.3 x 0.000001 N/sqm (10 to the minus 8th power torr) of gases and vapors other than mercury and less than 1.3 x 10 to the minus 8th N/sq m (10 to the minus 10th power torr) partial pressure of oxygen; also, it provided for mechanical sweeping of the liquid metal surfaces in the vacuum environment. The rates of evaporation of pure mercury and of dilute amalgams of tin (52 ppm), sodium (229 ppm), and lithium (165 ppm) were determined at temperature between 25 and 55 C both before and after 70 minute exposures to an approximately 270 N/sq m (2 torr) pressure of oxygen. The rates of evaporation of the pure mercury and the amalgams as first prepared were similar but the rates for the amalgams were reduced by at least 80% at 25 C as a result of the exposure to oxygen. The effect of the oxygen treatment could be completely removed by sweeping the amalgam surfaces. It was concluded that the reduced rates of evaporation resulted from the formation of transparent, insoluble, oxide films on the amalgam surfaces.

Frohnsdorff, G.↗
DOE OSTI2026

Plant-Nitrifier Interactions in Topsoil and Subsoil

Plants can influence soil microbes through resource acquisition and interference competition, with consequences for ecosystem function such as nitrification. However, how plants alter soil conditions to influence nitrifiers and nitrification rates remains poorly understood, especially in the subsoil. Here, coupling the 15N isotopic pool dilution technique, high throughput sequencing and in situ soil O2 monitoring, we investigated how a deep-rooted perennial grass, miscanthus, versus an adjacent shallow-rooted turfgrass reference shapes nitrifier assembly and function along 1 m soil profiles. In topsoil, the suppression of ammonia (NH3) oxidizing archaea (AOA) and gross nitrification rates in miscanthus relative to the reference likely resulted from nitrifiers being outcompeted by plant roots and heterotrophic bacteria for ammonium (NH4+). The stronger tripartite competition under miscanthus may have been caused in part by the lower soil organic matter (SOM) content, which supported lower gross nitrogen (N) mineralization, the major soil process that produces NH4+. In contrast, below 10 cm soil depth, significantly greater gross nitrification rates were observed in miscanthus compared to the reference. This was likely driven by the significantly lower oxygen (O2) in miscanthus than reference subsoil, which selected against aerobic heterotrophic bacteria but in favor of AOA. Overall, we found that plants can regulate AOA community structure and function through different mechanisms in topsoil and subsoil, with suppression of nitrification in topsoil and enhancement of nitrification in subsoil.

Field Data↗
DOE OSTI2023

Low-carbon fuels for spark-ignited engines: A comparative study of compressed natural gas and liquefied petroleum gas on a CFR engine with exhaust gas recirculation

Decades of work on low-carbon fuels have established their potential for substantial emissions reductions; however, their adoption is still limited by infrastructure concerns and engine efficiency deficits. As infrastructures have begun to evolve, research on strategies that maximize engine efficiency through interactions with fuel properties must also now take center place. This paper compares the performance, emissions, and combustion characteristics of two forefront low-carbon fuels: compressed natural gas (CNG) and liquefied petroleum gas (LPG) in a cooperative fuel research (CFR) engine over a range of compression ratios and engine loads. The effects of exhaust gas recirculation (EGR), end-gas auto-ignition, and a novel combustion control tool, the combustion intensity metric (CIM), were also evaluated at different stoichiometric engine operating conditions. In comparison to LPG, CNG operation demonstrated an extended knock-free regime, allowing engine operation at higher engine loads and compression ratios, but LPG operation exhibited enhanced combustion characteristics with higher peak pressures and faster apparent heat release rates (AHRR). LPG operation achieved higher brake thermal efficiencies and lower equivalent CO 2 emissions compared to CNG operation at the tested engine loads and compression ratios. LPG demonstrated significantly higher EGR tolerance limits compared to CNG, with a maximum of 28% EGR rate, compared to 23% for CNG. This improved EGR dilution tolerance was responsible for a 90% reduction in NOx emissions for LPG compared to a maximum of 70% with CNG. EGR dilution also exhibited more effective knock mitigation potential with LPG, suppressing knock intensity values by up to 98% and transitioning the engine operation towards normal combustion from heavy knocking conditions. As a result, the CIM was found to decrease burn durations and improve the quality of combustion by controlling the desired fraction of end-gas auto-ignition.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2024

Response of the Current Climate to Land‐Ocean Contrasts in Parameterized Cumulus Entrainment

Abstract Cumulus entrainment substantially regulates the earth's climate but remains poorly constrained in global climate models. Recent studies have shown that cumulus bulk entrainment (or dilution) is particularly sensitive to continentality, with the entrainment rate in simulated maritime cumuli nearly double that of continental cumuli. This study examines the impacts of such land–ocean entrainment contrasts on the current climate using 21‐year simulations with the Geophysical Fluid Dynamics Laboratory's High‐Resolution Atmospheric Model (HIRAM). In response to a 25% reduction in the HIRAM entrainment parameter c 0 over land, precipitation over tropical land regions increases by up to 40%. Along with directly facilitating enhanced convective precipitation, this c 0 reduction induces an increase in soil moisture, which may contribute to a further enhancement of convective precipitation over land. A 25% c 0 reduction over the oceans leads to more widespread modifications of convection patterns, with the strongest signal in the tropical Pacific. Deep convection shifts upstream (eastward) there, inducing enhanced large‐scale ascent over the central Pacific with compensating subsidence and reduced humidity and precipitation over the western Pacific (WP). Land–ocean variations in c 0 project onto the Pacific Walker circulation, with the 25% land reduction strengthening it by 4% and the 25% ocean reduction weakening it by 14%. These changes are driven by variations in convective and large‐scale stratiform heating over the Pacific. While reduced c 0 over land enhances diabatic heating in the Maritime Continent to strengthen the Walker circulation, reduced c 0 over the oceans decreases diabatic heating in the WP to weaken the Walker circulation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Nucleation of soot: experimental assessment of the role of polycyclic aromatic hydrocarbon (PAH) dimers

The irreversible dimerization of polycyclic aromatic hydrocarbons (PAHs) – typically pyrene (C 16 H 10 ) dimerization – is widely used in combustion chemistry models to describe the soot particle inception step. This study concerns itself with the detection and identification of dimers of flame-synthesized PAH radicals and closed-shell molecules and an experimental assessment of the role of these PAH dimers for the nucleation of soot. To this end, flame-generated species were extracted from an inverse co-flow flame of ethylene at atmospheric pressure and immediately diluted with excess nitrogen before the mixture was analyzed using flame-sampling tandem mass spectrometry with collision-induced fragmentation. Signal at m/z = 404.157 (C 32 H 20 ) and m/z = 452.157 (C 36 H 20 ) were detected and identified as dimers of closed-shell C 16 H 10 and C 18 H 10 monomers, respectively. A complex between a C 13 H 9 radical and a C 24 H 12 closed-shell PAH was observed at m/z = 465.164 (C 37 H 21 ). However, a rigorous analysis of the flame-sampled mass spectra as a function of the dilution ratio, defined as the ratio of the flow rates of the diluent nitrogen to the sampled gases, indicates that the observed dimers are not flame-born, but are produced in the sampling line. In agreement with theoretical considerations, this paper provides experimental evidence that pyrene dimers cannot be a key intermediate in particle inception at elevated flame temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Filtration of Hanford Tank 241-AN-107 Supernatant at 16 °C

Approximately 9 liters of supernatant from Hanford waste tank 241-AN-107 was delivered by Washington River Protection Solutions to the Radiochemical Processing Laboratory (RPL) at Pacific Northwest National Laboratory. The thirty-six AN-107 sample bottles consisted of six sets of six samples, with each set pulled from a unique tank sampling level. Prior to testing, samples from each level were composited to provide nominally level-independent feed for dead end filtration and ion exchange testing. The composited 241-AN-107 supernatant was chilled to 16 °C for 1 week prior to testing. Filtration testing was then conducted using a backpulse dead-end filter (BDEF) system equipped with a feed vessel and a Mott inline filter Model 6610 (Media Grade 5) in the hot cells of the RPL. The purpose of this testing is to a) demonstrate dead-end filtration (DEF) of AN-107 feed at reduced temperature to obtain prototypic tank side cesium removal (TSCR) flux rates and identify issues that may impact filtration after dilution to 5.5M Na, and b) provide feed for a follow on ion exchange unit operation. The feed was filtered through the BDEF system at a targeted flux of 0.065 gpm/ft 2 . During filtration the differential pressure required to effect filtration at 0.065 gpm/ft 2 was slow to increase for most of the filtration campaign. After all the feed bottles had been pumped into the slurry reservoir, the bottoms of the bottles were added to the reservoir and transmembrane pressure (TMP) reached 2.0 psid (the TSCR action limit). The prototypic filter cleaning process was unable to effectively restore filter performance, and cleaning with oxalic acid was required before flow through the filter could be restored. This indicates that the Media Grade 5 filter may require an alternative cleaning protocol when processing AN-107 supernatant. After completing filtration of the AN-107 feed, the filter was cleaned. Solids concentrated from the backpulse solutions were composed of natrophosphate, Mn-Fe phases, and fluoro-natrophosphate that occurred as particle agglomerates. The individual particles were in some cases 100s of micrometers across which is consistent with prior observations from AN-107 supernate waste characterizations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Ion-Selective Scattering Studied Using the Variable-Energy Electron Irradiation in the Ba 0.2 K 0.8 Fe 2 As 2 Superconductor

Low-temperature variable-energy electron irradiation was used to induce non-magnetic disorder in a single crystal of a hole-doped iron-based superconductor, Ba $1-x$ K $x$ Fe 2 As 2 , $x$ = 0.80. To avoid systematic errors, the beam energy was adjusted non-consequently for five values between 1.0 and 2.5 MeV when sample resistance was measured in situ at 22 K. For all energies, the resistivity raises linearly with the irradiation fluence suggesting the creation of uncorrelated dilute point-like disorder (confirmed by simulations). The rate of the resistivity increase peaks at energies below 1.5 MeV. Comparison with calculated partial cross-sections points to the predominant creation of defects in the iron sublattice. Simultaneously, superconducting $T_c$, measured separately between the irradiation runs, is monotonically suppressed as expected, since it depends on the total scattering rate, hence on the total cross-section, which is a monotonically increasing function of the energy. Our work experimentally confirms an often-made assumption of the dominant role of the iron sub-lattice in iron-based superconductors.

36 MATERIALS SCIENCE↗
NASA NTRS1978

Metastable states and mass loss in Be stars

Three strong asymmetric absorption features with short-wavelength wings extending 350 km/s from their respective line centers at 2061.6, 2068.2, and 2079.0 A appear in high-resolution UV spectral data (0.1 A) for the Be star Phi Per (B2 Ve4) obtained with the Balloon-borne Ultraviolet Stellar Spectrometer (BUSS) on the evening of September 16, 1976. These transitions are not resonance lines and have been identified as transitions of Fe III (UV 48) originating from a metastable state with an excitation of 5.01 eV. The relative populations of the metastable and ground states are independent of the dilution factor, allowing calculation of the mass-outflow rate for a generalized model. Thus, a mass-outflow rate of 5 hundred-billionths of a solar mass per year is obtained. These transitions are observable with IUE and represent an important tool for studying mass outflow in Be and shell stars.

Bruhweiler, F. C.↗
NASA NTRS2002

Tetragonal Lysozyme Nucleation and Crystal Growth: The Role of the Solution Phase

Lysozyme, and most particularly the tetragonal form of the protein, has become the default standard protein for use in macromolecule crystal nucleation and growth studies. There is a substantial body of experimental evidence, from this and other laboratories, that strongly suggests this proteins crystal nucleation and growth is by addition of associated species that are preformed by standard reversible concentration-driven self association processes in the bulk solution. The evidence includes high resolution AFM studies of the surface packing and of growth unit size at incorporation, fluorescence resonance energy transfer measurements of intermolecular distances in dilute solution, dialysis kinetics, and modeling of the growth rate data. We have developed a selfassociation model for the proteins crystal nucleation and growth. The model accounts for the obtained crystal symmetry, explains the observed surface structures, and shows the importance of the symmetry obtained by self-association in solution to the process as a whole. Further, it indicates that nucleation and crystal growth are not distinct mechanistically, but identical, with the primary difference being the probability that the particle will continue to grow or dissolve. This model also offers a possible mechanism for fluid flow effects on the growth process and how microgravity may affect it. While a single lysozyme molecule is relatively small (M.W. = 14,400), a structured octamer in the 4(sub 3) helix configuration (the proposed average sized growth unit) would have a M.W. = 115,000 and dimensions of 5.6 x 5.6 x 7.6 nm. Direct AFM measurements of growth unit incorporation indicate that units as wide as 11.2 nm and as long as 11.4 nm commonly attach to the crystal. These measurements were made at approximately saturation conditions, and they reflect the sizes of species that both added or desorbed from the crystal surface. The larger and less isotropic the associated species the more likely that it will be oriented to some degree in a flowing boundary layer, even at the low flow velocities measured about macromolecule crystals. Flow-driven effects resulting in misorientation upon addition to and incorporation into the crystal need only be a small fraction of a percentage to significantly affect the resulting crystal. One Earth, concentration gradient driven flow will maintain a high interfacial concentration, i.e., a high level (essentially that of the bulk solution) of solute association at the interface and higher growth rate. Higher growth rates mean an increased probability that misaligned growth units are trapped by subsequent growth layers before they can be desorbed and try again, or that the desorbing species will be smaller than the adsorbing species. In microgravity the extended diffusive boundary layer will lower the interfacial concentration. This results in a net dissociation of aggregated species that diffuse in from the bulk solution, i.e., smaller associated species, which are more likely able to make multiple attempts to correctly bind, yielding higher quality crystals.

Pusey, Marc L.↗
NASA NTRS1997

Continuous in vitro evolution of catalytic function

A population of RNA molecules that catalyze the template-directed ligation of RNA substrates was made to evolve in a continuous manner in the test tube. A simple serial transfer procedure was used to achieve approximately 300 successive rounds of catalysis and selective amplification in 52 hours. During this time, the population size was maintained against an overall dilution of 3 x 10(298). Both the catalytic rate and amplification rate of the RNAs improved substantially as a consequence of mutations that accumulated during the evolution process. Continuous in vitro evolution makes it possible to maintain laboratory "cultures" of catalytic molecules that can be perpetuated indefinitely.

Non-NASA Center↗
NASA NTRS1984

The chemical durability of tektites - A laboratory study and correlation with long-term corrosion behavior

Leach tests carried out on tektite specimens (indochinites and australites) under high-dilution conditions show a common behavior characterized by low leach rates (0.00018 g/sq m per d, or 7.2 x 10 to the -12th m/d at 23 C) and an activation energy of (79,600 + or - 700 J/mol). The extent of selective leaching is very small, of the order of 10 to the -8th m. Extrapolation of test results over the lifetime of the tektites gives an excellent agreement with field observations on the extent of corrosion, and this is an important step in establishing the validity of laboratory tests as a basis for the development of models and predictions concerning long-term durabilities at least in the limiting case of high dilution or rapid flow. The results are also shown to be in agreement with various previous observations on the corrosion resistance of tektites. The chemical durability of tektites is observed to be consistent with their composition, highlighting requirements of high corrosion resistance in glasses; these requirements include a silica content in excess of 67 mol percent, an extremely low water content, and an alkali content which is low both absolutely and relative to the di- and poly-valent metal oxide levels. It is shown that artificial glasses which fulfil these criteria are no less corrosion-resistant than the corresponding natural glasses. These conclusions have bearing on the development, as well as on the evaluation, of glasses intended for very long service, such as radioactive waste vitrification media.

Barkatt, A.↗
NASA NTRS2014

A Computational and Experimental Study of Coflow Laminar Methane/Air Diffusion Flames: Effects of Fuel Dilution, Inlet Velocity, and Gravity

The influences of fuel dilution, inlet velocity, and gravity on the shape and structure of laminar coflow CH4-air diffusion flames were investigated computationally and experimentally. A series of nitrogen-diluted flames measured in the Structure and Liftoff in Combustion Experiment (SLICE) on board the International Space Station was assessed numerically under microgravity (mu g) and normal gravity (1g) conditions with CH4 mole fraction ranging from 0.4 to 1.0 and average inlet velocity ranging from 23 to 90 cm/s. Computationally, the MC-Smooth vorticity-velocity formulation was employed to describe the reactive gaseous mixture, and soot evolution was modeled by sectional aerosol equations. The governing equations and boundary conditions were discretized on a two-dimensional computational domain by finite differences, and the resulting set of fully coupled, strongly nonlinear equations was solved simultaneously at all points using a damped, modified Newton's method. Experimentally, flame shape and soot temperature were determined by flame emission images recorded by a digital color camera. Very good agreement between computation and measurement was obtained, and the conclusions were as follows. (1) Buoyant and nonbuoyant luminous flame lengths are proportional to the mass flow rate of the fuel mixture; computed and measured nonbuoyant flames are noticeably longer than their 1g counterparts; the effect of fuel dilution on flame shape (i.e., flame length and flame radius) is negligible when the flame shape is normalized by the methane flow rate. (2) Buoyancy-induced reduction of the flame radius through radially inward convection near the flame front is demonstrated. (3) Buoyant and nonbuoyant flame structure is mainly controlled by the fuel mass flow rate, and the effects from fuel dilution and inlet velocity are secondary.

flames↗
DOE OSTI2020

Editors’ Choice—Flooded by Success: On the Role of Electrode Wettability in CO 2 Electrolyzers that Generate Liquid Products

Economic operation of carbon dioxide (CO 2 ) electrolyzers generating liquid products will likely require high reactant conversions and product concentrations, conditions anticipated to challenge existing gas diffusion electrodes (GDEs). Notably, electrode wettability will increase as lower surface tension products (e.g., formic acid, alcohols) are introduced into electrolyte streams, potentially leading to flooding. To understand the hydraulically stable operating envelopes in mixed aqueous-organic liquid domains, we connect intrinsic electrode wettability descriptors to operating parameters such as electrolyte flow rate and current. We first measure contact angles of water-organic product dilutions on polytetrafluoroethylene (PTFE) and graphite surfaces as planar analogues for GDE components. We then use material balances around the reactive gas-liquid-solid interface to calculate product mass fractions as functions of water sweep rate and current. Product composition maps visualize the extent to which changes in cell performance influence capillary pressure, a determinant of GDE saturation. Analyses suggest that formic acid mixtures pose little risk for GDE flooding across a wide range of conditions, but effluents containing <30% alcohol by mass may cause flooding. This study reveals opportunities to integrate microstructural features and oleophobic surface treatments into GDEs to repel aqueous-organic mixtures and expand the window of stable operating conditions.

25 ENERGY STORAGE↗
DOE OSTI2020

Dust Growth by Accretion of Molecules in Supersonic Interstellar Turbulence

We show that the growth rate of dust grains in cold molecular clouds is enhanced by the high degree of compressibility of a turbulent, dilute gas. By means of high-resolution (1024 3 ) numerical simulations, we confirm the theory that the spatial mean growth rate is proportional to the gas-density variance. This also results in broadening of the grain-size distribution (GSD) due to turbulence-induced variation of the grain-growth rate. We show, for the first time in a detailed numerical simulation of hydrodynamic turbulence, that the GSD evolves toward a shape that is a reflection of the gas-density distribution, regardless of the initial distribution. That is, in case of isothermal, rotationally forced turbulence, the GSD tends to be a lognormal distribution. We also show that in hypersonic turbulence, decoupling of gas and dust becomes important and that this leads to an even further accelerated grain growth.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Theoretical and kinetic modeling study of H 2 S pyrolysis

Hydrogen sulfide pyrolysis was investigated theoretically and through chemical kinetic modeling. Reactions on the SHH potential energy surface, primarily S + H 2 (+Ar) ⇌ H 2 S (+ Ar) (R1) and S + H 2 ⇌ SH + H (R6b) were characterized by ab initio calculations. Results for k 1 were in good agreement with experiment, but deviated strongly below 2000 K from values previously used in modeling. Collider efficiencies for H 2 S, S 2 , and N 2 compared to Ar were calculated for R1. Hydrogen sulfide decomposition experiments reported in literature were re-examined in terms of an updated detailed chemical kinetic model. Concentration profiles for the atomic S at high temperature in shock tubes supported the present value of k 1 and served to constrain the rate constants for reaction of S with SH and H 2 S. To explain results from batch and flow reactors, conducted at high H 2 S concentrations in the 900–1400 K range, a very fast rate constant was required for HSS + H ⇌ SH + SH. Under dilute conditions, the gas-phase chemistry was too slow to compete and the decomposition of H 2 S was controlled by loss on the reactor surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

In Situ Analysis of Electron-Induced Chemical Transformations in Vapor-Phase-Synthesized Al-Based Inorganic–Organic Hybrid Thin Films for EUV Resist Platform

The rapid advancement and stringent requirements of extreme ultraviolet (EUV) lithography technology necessitate the development of advanced photoresist systems for next-generation microelectronics. Recent studies have demonstrated that inorganic-based hybrid photoresists offer notable improvements in EUV sensitivity, etch resistance, and greater insusceptibility to pattern collapse compared to their purely organic counterparts. However, variations in the synthesis/coating approaches and chemistry of inorganic–organic photoresists can result in distinct exposure mechanisms. In this work, an Al-based hybrid thin film resist system synthesized via molecular (atomic) layer deposition (MLD or MALD) is explored, focusing on its electron-beam and EUV patterning mechanisms. The Al-based hybrid thin films are deposited using trimethylaluminum (TMA) and the organic precursor hydroquinone, exhibiting a saturated growth rate within the temperature range of 150–200°C. In diluted tetramethylammonium hydroxide (TMAH)-based developer solutions, the electron-irradiated Al-based hybrid thin film system behaves as a negative tone resist, achieving a sensitivity of 10.4 mC/cm 2 at 0.1 kV electron beam lithography (EBL). Chemical changes induced by electron exposure are also analyzed in this study using X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and a unique infrared spectroscopy setup, revealing the potential cross-linking pathways. To further correlate the electron-induced chemical transformations with those mediated by EUV irradiations, a combination of X-ray photoemission electron microscopy/low-energy electron microscopy (XPEEM/LEEM) system is also employed. In conclusion, this study provides critical insights into the mechanisms underlying solubility switching and contributes to the design of advanced resist materials for EUV lithography.

36 MATERIALS SCIENCE↗