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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 865 records · Page 48
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Bio‐Inspired Cascade Photocatalysis on Fe Single‐Atom Carbon Nitride Upcycles Plastic Wastes for Effective Acetic Acid Production

Plastic imposes a critical threat to the environment, ecosystems, and human health because of the low utilization efficiency of plastics. Here, we demonstrate a sustainable, highly efficient cascade photocatalysis for upcycle plastics to value-added acetic acid using Fe single-atom catalysts (Fe@C 3 N 4 SAC) at ambient conditions. Inspired by Phanerochaete chrysosporium microbial, the defective Fe@C 3 N 4 SAC acts as a bifunctional cascade photocatalyst for both Fenton-like and CO 2 reduction reactions. During the reaction, hydroxyl radicals (*OH) form and subsequently oxidize plastics into CO 2 intermediates. These CO 2 intermediates are then photo-reduced to CH 3 COOH on the same catalyst via cascade photocatalysis. The mechanism is confirmed by in situ multimodal microscopy and spectroscopies, with density functional theory calculations. A state-of-art CH 3 COOH yield of 63.8 mg h −1 gcat −1 from PVC, 12.7 mg h −1 gcat −1 from PE, 5.4 mg h −1 gcat −1 from PET, and 5.3 mg h −1 gcat −1 from PP are directly obtained under AM1.5G solar irradiation and further validated under real sunlight (≈0.6 sun), achieving 5.6 mg h −1 gcat −1 from PET, using low-cost Fe@C 3 N 4 SAC in a sealed reactor by enhancing the photon transport and utilization efficiency. The techno-economic analysis shows it is promising to practically mitigate plastic based on broader social welfare assessments.

cascade photocatalysis↗
DOE OSTI2023

Engineering the fracture resistance of 2H-transition metal dichalcogenides using vacancies: An in-silico investigation based on HRTEM images

Vacancy engineering of 2H-transition metal dichalcogenides (2H-TMDs) has recently attracted great attention due to its potential to fine-tune the phonon and opto-electric properties of these materials. From a mechanical perspective, this symmetry-breaking process typically reduces the overall crack resistance of the material and adversely affects its reliability. However, vacancies can trigger the formation of heterogeneous phases that synergistically improve fracture properties. In this study, using MoSe2 as an example, we characterize the types and density of vacancies that can emerge under electron irradiation and quantify their effect on fracture. Molecular dynamic (MD) simulations, employing a re-parameterized Tersoff potential capable of accurately capturing bond dissociation and structural phase changes, reveal that isolated transition metal monovacancies or chalcogenide divacancies tend to arrest the crack tip and hence enhance the monolayer toughness. In contrast, isolated chalcogenide monovacancies do not significantly affect toughness. The investigation further reveals that selenium vacancy lines, formed by high electron dose rates, alter the crack propagating direction and lead to multiple crack kinking. Using atomic displacements and virial stresses together with a continuum mapping, displacement, strain, and stress fields are computed to extract mechanistic information, e.g., conditions for crack kinking and size effects in fracture events. The study also reveals the potential of specific defect patterns, “vacancy engineering,” to improve the toughness of 2H-TMDs materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Command of active and responsive elastomers by topological defects and patterns

The project resulted in the development of stimuli-responsive elastomer coatings formed by photopolymerized liquid crystal molecules. The molecular orientation of the liquid crystal elastomers is coupled to rubber-like elasticity. The project developed an approach to produce complex patterns of molecular orientation in elastomers by employing photopatterning technique based on plasmonic metamasks that convert unpolarized incoming light into a transmitted light beam with spatially-varying linear polarization. The polarization-modulated light beam aligns the film of azodye molecules, which serves as the substrate for liquid crystal elastomer coating. The alignment of the azodye molecules follows the polarization pattern with a phase shift of the alignment direction by 90 degrees. The azodye substrate imposes orientation of molecules in the adjacent liquid crystal layer which is preserved after the monomers are polymerized into a liquid crystal elastomer. By using differently aligned substrates one could produce various patterns of molecular orientation in the elastomer, which dictate the mechanical properties of the elastomers and their response to external stimuli such as temperature, humidity, and ultraviolet irradiation. In particular, the predesigned molecular orientation produces deterministically defined topography response of the liquid crystal coatings, in which their free surface changes from flat to either locally elevated or locally compressed, depending on whether the pre-inscribed molecular orientation is predesigned with a splay or bend deformation. The research established that the mechanism of this deterministic relation between the dynamic topography and pre-inscribed molecular orientation is rooted in the change of the tensorial order parameter that characterizes the degree of orientational order, and in the contraction/expansion of polymer molecules in response to the order parameter changes. In particular, lowering the order causes contraction of polymer globules. The work demonstrated that the dynamic topography of elastomer coatings with three-dimensional pattern of orientational order includes up and down motion of the material (along the normal to the coating) and also shifts in lateral directions. We demonstrate that the deterministic relationship between the orientational patterns and variations of coatings’ profile is caused by forces that are mathematically equivalent to active forces in the system of “pullers” or “pushers” in active matter, demonstrating universality of the out-of-equilibrium behavior. The project resulted in theoretical models that predictively describe the dynamic response of coatings. The topography of liquid crystal elastomers is sensitive to stimuli such as temperature, ultraviolet irradiation, and humidity. The applicability of the patterned approach to produce dynamic coatings was expanded from nematic elastomers to their smectic counterparts. The project combined a battery of imaging techniques to unveil the dynamic properties of the coatings, ranging from the state-of-the-art dynamic holographic microscopy to fluorescent confocal polarizing microscopy and polscope microscopy. The research uncovered potential applications of dynamic elastomer coatings, such as control placement of colloidal particles, engineering of living tissues with alignment patterns of cells that follow the orientational order of elastomer coatings. The approach developed in the project can be used to design programmable dynamic coatings with functionalities that mimic biological tissues such as skin.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Effects of irradiation damage on the hardness and elastic properties of quaternary and high entropy transition metal diborides

Multi-principal component transition metal (TM) diborides represent a class of high-entropy ceramics (HECs) that have received considerable interest in recent years owing to their promising properties for extreme environment applications that include thermal/ environmental barriers, hypersonic vehicles, turbine engines, and next-generation nuclear reactors. While the addition of chemical disorder through the random distribution of TM elements on the cation sublattice has offered opportunities to tailor elastic stiffness and hardness, the effects of irradiation-induced structural damage on the physical properties of these complex materials have remained largely unexplored. To this end, changes in the hardness and elastic moduli of a high-entropy TM diboride (Hf 0.2 Nb 0.2 Ta 0.2 Ti 0.2 Zr 0.2 )B 2 and three of its quaternary subsets following irradiation with 10 MeV gold (Au) ions to fluences of up to 6 × 10 15 Au cm -2 are investigated at the micrometer and sub-micrometer length-scales via the dispersion of laser-generated surface acoustic waves (SAW) and nanoindentation, respectively. The nanoindentation measurements show that the TM diborides exhibit an initial increase in hardness following irradiation with energetic Au ions, with a subsequent decrease in hardness following further irradiation. One quaternary composition, (Hf 1/3 Ta 1/3 Ti 1/3 )B 2 , exhibits a notable exception to the trend and continues to exhibit an increase in hardness with ion irradiation fluence. Although differences in the absolute values of the effective elastic moduli obtained from the measured SAW dispersion and nanoindentation are observed (and attributed to microstructural variations at the measurement length-scale), both techniques yield similar trends in the form of an initial reduction and subsequent saturation in the elastic modulus with increasing ion irradiation fluence. The quaternary TM diboride (Hf 1/3 Ta 1/3 Ti 1/3 )B 2 again exhibits a departure from this trend. The high-entropy TM diboride (Hf 0.2 Nb 0.2 Ta 0.2 Ti 0.2 Zr 0.2 )B 2 exhibits the greatest recovery in hardness and modulus when irradiated to high ion fluences following initial changes at low fluence, indicating superior resistance to radiation-induced damage over its quaternary counterparts. Opportunities for designing HECs with superior hardness and modulus for enhanced radiation resistance (compared to their single constituent counterparts) by tailoring chemical disorder and bond character in the lattice are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Impact of Coating Defects on Performance of Coated Zirconium Cladding

Research on accident tolerant fuels (ATF) has started after the Fukushima accident [1–3]. While efforts have been expended on both fuel and cladding ATF concepts, the bulk of work has been devoted to improved cladding. The overarching goal of these approaches is to extend the coping time available during a severe accident before any event would result in release of radioactivity to the public. The most basic ATF cladding concept is obtained by applying a thin coating of highly corrosion-resistant material on the surface of a licensed zirconium cladding alloy. This thin coating is intended to not interfere with the neutronic or mechanical performance of the base cladding under normal operating conditions. Different coating materials, thicknesses, coating processes, process parameters, and testing methods have an impact on the microstructure and mechanical properties and therefore on the results of the applied investigation methods. These challenges have motivated an initial focus on demonstrating that the presence of coatings do not perturb the critical performance benchmarks of uncoated material. Ongoing lead test assembly irradiations of coated zirconium concepts in commercial reactions is intended to establish baseline performance in this regard in the coming years.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Understanding spectral dependance of laser-induced damage precursors in dielectric materials (Full report_23-ERD-006)

The performance of high-energy laser systems is constrained by laser-induced damage in dielectric coatings, particularly those containing hafnium oxide (HfO 2 ). While thresholds at fundamental Nd harmonics are well studied, the spectral dependence of damage initiation—especially under dual-wavelength irradiation—remains poorly characterized. This project provides the first systematic investigation of wavelength-dependent laser damage in hafnia coatings, focusing on nanoscale precursors such as craze lines, nanobubbles, stoichiometric variations, nodules, and controlled crystallization. Coatings were fabricated via ion beam sputtering and electron-beam deposition and characterized using spectrophotometry, ellipsometry, AFM, GI-XRD, RBS, PCI absorption, and fs/ns laser damage testing. Results show that craze lines, benign under infrared light, strongly initiate damage under UV due to wavelength-selective field intensification. Substituting xenon for argon suppresses nanobubbles and improves UV thresholds by up to 32%. Oxygen modulation reveals that fully oxidized films maximize UV resistance, though at the cost of porosity and stress in multilayers. HfO 2 –SiO 2 composites resist crystallization and defects while achieving ppm-level absorption and elevated thresholds, whereas full crystallization of HfO 2 enhances LIDT by reducing defects and improving thermal transport. Collectively, these findings link photon energy, defect states, and bandgap collapse, providing a predictive framework for wavelength-dependent laser damage. The outcomes directly inform the design of durable, multi-wavelength coatings for facilities such as NIF, MEC, HAPLS, and DPAL, advancing the readiness of next-generation optics.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Plasmon assisted synthesis of TiN-supported single-atom nickel catalysts

We report the deposition of single atom nickel catalyst on refractory plasmonic titanium nitride (TiN) nanomaterials supports using the wet synthesis method under visible light irradiation. TiN nanoparticles efficiently absorb visible light to generate photoexcited electrons and holes. Photoexcited electrons reduce nickel precursor to deposit Ni atoms on TiN nanoparticles’ surface. The generated hot holes are scavenged by the methanol. We studied the Ni deposition on TiN nanoparticles by varying light intensity, light exposure time, and metal precursor concentration. These studies confirmed the photodeposition method is driven by hot electrons and helped us to find optimum synthesis conditions for single atoms deposition. We characterized the nanocatalysts using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), energy dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). We used density functional theory (DFT) calculations to predict favorable deposition sites and aggregation energy of Ni atoms on TiN. Surface defect sites of TiN are most favorable for single nickel atoms depositions. Interestingly, the oxygen sites on native surface oxide layer of TiN also exhibit strong binding with the single Ni atoms. Plasmon enhanced synthesis method can facilitate photodeposition of single atom catalysts on a wide class of metallic supports with plasmonic properties.

36 MATERIALS SCIENCE↗
NASA NTRS2005

Protective effect of apigenin on radiation-induced chromosomal damage in human lymphocytes

The potential use of flavonoids as a radioprotector is of increasing interest because of their high antioxidant activity and abundance in the diet. The aim of this study is to examine genotoxic and radioprotective effects of one of the most common flavonoids, apigenin, on radiation-induced chromosome aberrations in human lymphocytes. The cytokinesis-block micronucleus (CBMN) assay was used to evaluate such effects of apigenin. Blood samples were collected from two non-smoking healthy male volunteers who had no history of previous exposure to other clastogenic agents. Isolated lymphocytes were cultured. There were two tubes per concentration for all treatments. To evaluate the genotoxicity of apigenin, cells were first treated with different concentrations of apigenin (0, 2.5, 5, 10 and 25 microg/mL) at 24 h after culture initiation, followed by cytochalasin-B (Cyt-B) treatment (3 microg/mL) and cell harvest at 44 and 72 h, respectively. Secondly, to investigate the radioprotective effect, cell cultures were exposed to different concentrations of apigenin as described above for 30 min before being irradiated to 2 Gy of 137Cs gamma rays (at a dose rate of 0.75 Gy/min). In all instances, the frequency of MN was scored in binucleated (BN) cells. The nuclear proliferation index also was calculated. We did not detect an increase in the frequency of MN in non-irradiated human lymphocyte cultures treated with 2.5, 5.0 or 10 microg/mL apigenin; although, we did observe an increase in cultures treated with 25 microg/mL apigenin (the highest concentration of apigenin used in our study). We also observed a significant increase in the frequency of MN in irradiated cells overall; however, the frequency was decreased as the concentration of apigenin increased, suggesting a radioprotective effect. These findings provide a basis for additional studies to help clarify the potential use and benefit of apigenin as a radioprotector.

NASA Discipline Radiation Health↗
DOE OSTI2023

Two-dimensional spin systems in PECVD-grown diamond with tunable density and long coherence for enhanced quantum sensing and simulation

Systems of spins engineered with tunable density and reduced dimensionality enable a number of advancements in quantum sensing and simulation. Defects in diamond, such as nitrogen-vacancy (NV) centers and substitutional nitrogen (P1 centers), are particularly promising solid-state platforms to explore. However, the ability to controllably create coherent, two-dimensional spin systems and characterize their properties, such as density, depth confinement, and coherence, is an outstanding materials challenge. We present a refined approach to engineer dense (≳1 ppm ∙ nm), 2D nitrogen, and NV layers in diamond using delta-doping during plasma-enhanced chemical vapor deposition epitaxial growth. We employ both traditional materials techniques, e.g., secondary ion mass spectrometry, alongside NV spin decoherence-based measurements to characterize the density and dimensionality of the P1 and NV layers. We find P1 densities of 5–10 ppm ∙ nm, NV densities between 1 and 3.5 ppm ∙ nm tuned via electron irradiation dosage, and depth confinement of the spin layer down to 1.6 nm. We also observe high (up to 0.74) ratios of NV to P1 centers and reproducibly long NV coherence times, dominated by dipolar interactions with the engineered P1 and NV spin baths.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Effect of Cr and Al on Elastic Constants of FeCrAl Alloys Investigated by Molecular Dynamics Method

The FeCrAl alloy system is recognized as one of the candidate materials for accident-tolerant fuel (ATF) cladding in the nuclear power industry due to its high oxidation resistance under irradiation and high-temperature environments. The concentrations of Cr and Al have a significant effect on elastic properties of the FeCrAl alloy. In this work, elastic constants C 11 , C 12 , C 44 , bulk modulus and shear modulus of FeCrAl alloy were calculated with molecular dynamics methods. We explored compositions with 1–15 wt.% Cr and 1–5 wt.% Al at temperatures from 0 K to 750 K. The results show that the concentrations of Al and Cr have different effects on the elastic constants. When the concentration of Al was fixed, a decrease in bulk modulus and shear modulus with increasing Cr content was observed, consistent with previous experimental results. The dependence of elastic constants on temperature was also the same as in the experiments. Investigations into elastic properties of defect-containing alloys have shown that vacancies, voids, interstitials and Cr-rich precipitations have different effects on elastic properties of FeCrAl alloys. Investigations of elastic properties of defect-containing alloys have shown that vacancies, void, interstitials and Cr-rich precipitations have different effects on elastic properties of FeCrAl alloys. Therefore, the present results indicate that both the Cr and Al concentrations and radiation defects should be considered to develop and apply the FeCrAl alloy in ATF design.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Photocurrent in carbon nanotube bundle: Graded Seebeck coefficient phenomenon

Here, polarized photovoltage of a suspended aligned carbon nanotube (CNT) bundle under uniform optical irradiation is discovered without additional structural modification or bias voltage. Such a phenomenon is very surprising considering the metallic behavior of the overall bundle and zero temperature difference between ends. The photovoltage characteristic time is found similar to the thermal response time under step Joule heating and implies a relation to the thermal behavior of the CNT bundle. A similar thermoelectric voltage is also observed during step Joule heating. Localized laser heating and scanning along the axial direction of the bundle uncovers a linear spatial variation of the local Seebeck coefficient. The Seebeck coefficient linearly decreases from root to tip of the CNT bundle with a rate of a few - µV∙K –1 ·mm –1 . Deep investigation in both the microscopic and macroscopic structures of the CNT bundle reveals that the local alignment of CNT assemblies rather than the minor defects in individual CNTs brings about this linear distribution of Seebeck coefficient in space. The finding presents a new way for direct photon-to-electric energy conversion via Seebeck coefficient grading in CNT structures.

42 ENGINEERING↗
DOE OSTI2020

Characterization of Partial Charge Collection Induced by Neutron Damage in High-Purity Germanium Detectors

This paper investigates the correlation of damage induced by neutron interactions and degradation in the spectra of HPGe detectors. As neutrons kinetically interact with germanium crystals, they create interstitial and vacancy defects within the lattice. These defects then interfere with the charge migration of electron-hole pairs and reduce resolution in the observed energy spectrum. The partial charge collection produces observable spectral changes by increasing the peak width and reducing resolution (full width half maximum). A detailed characterization using various check sources was performed before and after iterations of neutron exposure in order to observe the effects of the neutron damage. An additional set of measurements was performed along with characterizations to show the detector’s response at discrete locations on the HPGe crystal. This was done to observe how the spectrum changes when the gamma rays are isolated to regions of various thicknesses of germanium. In order to impart damage, the detector was placed inside a californium shuffler with the face of the detector against the guide tube for the 252 Cf source. For irradiation of the HPGe, the source was then positioned in front of the face of the detector using the stepper motor of the shuffler. The neutron exposure time intervals were recorded and increased based on the initial damage observed. An MCNP simulation was performed to estimate the amount of interactions that occurred in the germanium crystal to ensure enough damage had occurred. Studying the effects that neutron damage imparts on a bullet-type HPGe detector can help provide necessary data to estimate total neutron exposure limits, reduce the likelihood of decisions made on suspect data, and aid in diagnostics of a damaged detector.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Kinetic Simulations of Microstructural Evolution (KSOME)

"Kinetic simulations of microstructural evolution" (KSOME) is an object Kinetic Monte Carlo (OMKC) simulation code. It is developed to simulate microstructural evolution in materials during irradiation. KSOME is developed from ground up with priority given to the flexibility, ease of upgradability, and computation efficiency, in that order. With previously developed simulation codes, various processes (more precisely, the diffusion-reaction processes) that can occur in a system were hardwired into the code. Hence, to perform higher fidelity simulations, a significant coding effort was required every time to incorporate either a more accurate description of existing processes or new processes. With KSOME, the necessity for frequent code upgrades whenever there is a need to perform higher fidelity simulations is either eliminated or reduced significantly. In KSOME, the categories of various diffusion-reaction processes and the data-management system are hardwired, while the execution of the diffusion-reaction processes specific to a system is specified via input files. In the present version of KSOME, the analytical expression required to calculate defect interaction radii are inputted via a text file. However, the ability to parse mathematical expressions from a text file can be extended to input the analytical expression to calculate other defect properties; including the expressions to calculate the change in the migration barriers of mobile defects due to long-range interaction with extended defects

Nandipati, Giridhar [Pacific Northwest National La↗
NASA NTRS2009

Irradiation with molecular hydrogen as an accelerated total dose hardness assurance test method for bipolar linear circuits

High dose rate irradiation with hydrogen stress is proposed as an accelerated total dose test method for bipolar linear circuits. The method is validated across process and circuit technologies with five parts that are commonly used in space: a comparator (LM193 from National Semi-conductor), a voltage regulator (HSYE-117 RH from Intersil), a voltage reference (LT1019 from Linear Technology), a JFET input op amp (OP42 from Analog Devices) and a temperature transducer (AD590 from Analog Devices). The testing technique could rapidly establish an upper bound to the low dose rate response of parts in space and help with the part selection process in the design phase of a mission. The technology dependence and the viability of this technique are qualitatively explored using a physical model describing the dose rate response and the effect of hydrogen in bipolar technologies. The model uses four core processes: 1) space charge effects, 2) free electron/hole pair recombination, hole-hydrogen defect reactions in the oxides and 4) proton depassivation of dangling bonds at the Si/SiO2 interface. Radiation hardness assurance implications are discussed.

Pease, Ron↗
DOE OSTI2025

Chromium-doped uranium dioxide fuels: A review

UO 2 doped with parts per million CR 2 O 3 powder is considered a potential near term accident tolerant fuel candidate. Here, the results of decades of industry and academic research into Cr-doped UO 2 are analyzed and their shortcomings are critiqued. Focusing on the incorporation mechanisms of Cr into the fuel matrix, we explore a mechanistic understanding of the characteristic properties of Cr-doped UO 2 , notably, enhanced fission gas retention attributed to enlarged grain sizes following sintering, along with marginal improvements in the thermophysical properties. The findings of recent X-ray Adsorption Near Edge Spectroscopy studies were compared and put into conversation with historic data regarding the incorporation of Cr in UO 2 . On the basis of defect mechanisms, the case is made for the substitutional incorporation of Cr governing the lattice solubility but not the enhanced U diffusivity. Instead, Cr/CR 2 O 3 redox chemistry in a well-defined oxygen potential explains the differences in the U diffusivity and O/M ratio. The primary mechanism of doping enhanced grain growth is found to be liquid assisted sintering due to a CRO (1) eutectic phase at the grain boundaries. The role of inhomogeneities in Cr concentration in UO 2 at various length scales across the materials microstructure is highlighted and connected to promising experimental and modeling work to fill in the gaps in the current understanding of Cr-doped UO 2 . The review considers both the open scientific questions and engineering applications to illustrate the deep connections between the practice and theory in the design of accident tolerant nuclear fuels. In conclusion, the review ends with an outline of future works that combine meticulous irradiation studies and high resolution experiments with next generation modeling and simulations techniques empowered by machine learning advances to accelerate the fabrication and adoption of Cr-doped UO 2 light water reactors.

Cleveland, Mack Wesley [Massachusetts Inst. of Tec↗
DOE OSTI2022

Implications of Microstructure in Helium-Implanted Nanocrystalline Metals

Helium bubbles are known to form in nuclear reactor structural components when displacement damage occurs in conjunction with helium exposure and/or transmutation. If left unchecked, bubble production can cause swelling, blistering, and embrittlement, all of which substantially degrade materials and—moreover—diminish mechanical properties. On the mission to produce more robust materials, nanocrystalline (NC) metals show great potential and are postulated to exhibit superior radiation resistance due to their high defect and particle sink densities; however, much is still unknown about the mechanisms of defect evolution in these systems under extreme conditions. Here, the performances of NC nickel (Ni) and iron (Fe) are investigated under helium bombardment via transmission electron microscopy (TEM). Bubble density statistics are measured as a function of grain size in specimens implanted under similar conditions. While the overall trends revealed an increase in bubble density up to saturation in both samples, bubble density in Fe was over 300% greater than in Ni. To interrogate the kinetics of helium diffusion and trapping, a rate theory model is developed that substantiates that helium is more readily captured within grains in helium-vacancy complexes in NC Fe, whereas helium is more prone to traversing the grain matrices and migrating to GBs in NC Ni. Our results suggest that (1) grain boundaries can affect bubble swelling in grain matrices significantly and can have a dominant effect over crystal structure, and (2) an NC-Ni-based material can yield superior resistance to irradiation-induced bubble growth compared to an NC-Fe-based material and exhibits high potential for use in extreme environments where swelling due to He bubble formation is of significant concern.

36 MATERIALS SCIENCE↗
DOE OSTI2020

High-Resolution Three-Dimensional Sculpting of Two-Dimensional Graphene Oxide by E-Beam Direct Write

On demand switchable additive/subtractive patterning of 2D nanomaterials is an essential capability for developing new concepts of functional nanomaterials and their device realizations. Traditionally, this is performed via a multi-step process using photoresist coating and patterning by conventional photo or electron beam lithography, which is followed by bulk dry/wet etch or deposition. This limits the range of functionalities and structural topologies that can be achieved, as well as increases the complexity, cost, and possibility of contamination which are significant barriers to device fabrication from highly sensitive 2D materials. Focused electron beam induced processing (FEBIP) enables a material chemistry/site-specific, high-resolution multi-mode atomic scale processing and provides unprecedented opportunities for direct-write, single-step surface patterning of 2D nanomaterials with an in-situ imaging capability. It allows for realizing a rapid multi-scale/multi-mode approach, ranging from an atomic scale manipulation (e.g., via targeted defect introduction as an active site) to a large-area surface modification on nano and micro scales, including patterned doping and material removal/deposition with 2D (in-plane)/3D (out-of-plane) control. In this work, we report on a new capability of FEBIP for nanoscale patterning of graphene oxide via removal of oxygenated carbon moieties with no use of reactive gas required for etching complemented by carbon atom deposition using focused electron beam. The mechanism of experimentally observed phenomena is explored using the density functional theory (DFT) calculations, revealing that interactions of e-beam liberated reactive oxygen radicals with carbon atoms on graphene basal plane lead to creation of atomic vacancies in the material. The reaction by-products are volatile carbon di-oxides, which are dissociated and volatilized from the graphene oxide surface functional groups by interactions with an energetic focused electron beam. Along with selective “subtractive” patterning of graphene oxide, the same electron beam with increased irradiation doses can deposit out-of-plane 3D carbon nanostructures on top of or around the 2D etched pattern, thus forming a hybrid 2D/3D nanocomposite with feature control down to a few nanometers. Furthermore, this in-operando dual nanofabrication capability of FEBIP is unmatched by any other nanopatterning techniques and opens a new design window for forming 2D/3D complex nanostructures and functional nanodevices.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Nanometer Resolution Structure‐Emission Correlation of Individual Quantum Emitters via Enhanced Cathodoluminescence in Twisted Hexagonal Boron Nitride

Understanding the atomic structure of quantum emitters, often originating from point defects or impuritie, is essential for designing and optimizing materials for quantum technologies such as quantum computing, communication, and sensing. Despite the availability of atomic-resolution scanning transmission electron microscopy and nanoscale cathodoluminescence microscopy, experimentally determining the atomic structure of individual emitters is challenging due to the conflicting needs for thick samples to generate strong cathodoluminescence signals and thin samples for structural analysis. To overcome this challenge, significantly enhanced cathodoluminescence at twisted interfaces is leveraged to achieve sub-nanometer localization precision for the first time in mapping individual quantum emitters in carbon-implanted hexagonal boron nitride. This unprecedent spatial sensitivity, together with correlative electron energy loss spectroscopy quantitative scanning transmission electron microscopy imaging, and first principles density functional theory calculations, enables the identification of the atomic structure of the 440 nm blue emitter in hexagonal boron nitride as a substituted vertical carbon dimer. Building on the atomic structure insights, nanoscale spatially precise creation of blue emitters is demonstrated by electron beam irradiation of carbon-coated hexagonal boron nitride. This advancement in correlating atomic structures with optical properties lays the foundation for a deeper understanding and precise engineering of quantum emitters, significantly advancing the development of cutting-edge quantum information technologies.

2D material↗