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At least 73 records · Page 4

Measuring Loss Tangents of Substrates for Superconducting Qubits with Part-per-Billion Precision

We report precision measurements of dielectric loss tangents in substrates for superconducting qubits using an ultra-high quality factor niobium SRF cavity operating at millikelvin temperatures and low electric fields. Multiple substrate types and surface treatments are compared to assess how processing impacts microwave dissipation. The RF results are correlated with materials analysis, including ToF-SIMS and XPS, to identify dominant loss mechanisms. This combined study links microscopic surface chemistry to macroscopic performance and provides a framework for materials-driven improvements in qubit coherence and device design.

Bafia, Daniel [Fermilab]

Impact of Annealing on Superconducting Properties of Tantalum Thin Films

The pursuit for higher-coherence superconducting qubits has led to the adoption of new materials and innovative fabrication techniques. Among the commonly used superconducting materials, tantalum-based or tantalum-capped superconducting qubits have demonstrated the longest lifetimes, outperforming niobium devices even in the presence of their native oxides. Given the losses introduced by the surface oxide, one method to further improve performance is to reduce or eliminate the native oxide on tantalum through UHV annealing. In this work, we examine the effect of dissolved oxygen as a function of annealing temperature on the superconducting properties of tantalum thin films. Dissolved oxygen is quantified using atom probe tomography (APT) and secondary ion mass spectrometry (TOF-SIMS) and correlated with electromagnetic transport measurements performed using a Physical Property Measurement System (PPMS). This study observes that annealing decomposes the native oxide and drives oxygen diffusion into the film matrix. Increasing oxygen content decreases the superconducting transition temperature (Tc) and the residual resistivity ratio (RRR). The critical field decreases with the incorporation of oxygen, while the film’s coherence length decreases relatively by 5%. These results, as well as findings from ongoing studies linking fabrication processes to the structural and chemical properties of the superconducting film and Josephson junction, provide insight into effective strategies for improving the performance of superconducting devices.

Shinde, Maithilee [IIT, Chicago; Fermilab]

Measuring Loss Tangents of Substrates for Superconducting Qubits with Part-per-Billion Precision

We report precision measurements of dielectric loss tangents in substrates for superconducting qubits using an ultra-high quality factor niobium SRF cavity operating at millikelvin temperatures and low electric fields. Multiple substrate types and surface treatments are compared to assess how processing impacts microwave dissipation. The RF results are correlated with materials analysis, including ToF-SIMS and XPS, to identify dominant loss mechanisms. This combined study links microscopic surface chemistry to macroscopic performance and provides a framework for materials-driven improvements in qubit coherence and device design.

Bafia, Daniel [Fermilab]

Electrical Behavior of Combinatorial Thin-Film Zr x Ta 1−x O y

Combinatorial magnetron sputtering and electrical characterization were used to systematically study the impact of compositional changes in the resistive switching of transition metal oxides, specifically the Zr x Ta 1−x O y system. Current-voltage behavior across a range of temperatures provided insights into the mechanisms that contribute to differences in the electrical conductivity of the pristine Ta 2 O 5 and ZrO 2 , and mixed Zr x Ta 1−x O y devices. The underlying conductive mechanism was found to be a mixture of charge trapping and ionic motion, where charge trapping/emission dictated the short-term cycling behavior while ion motion contributed to changes in the conduction with increased cycling number. ToF-SIMS was used to identify the origin of the “wake-up” behavior of the devices, revealing an ionic motion contribution. This understanding of how cation concentration affects conduction in mixed valence systems helps provide a foundation for a new approach toward manipulating resistive switching in these active layer materials.

36 MATERIALS SCIENCE

African dust transported to Barbados in the wintertime lacks indicators of chemical aging

The chemical processing (“aging”) of mineral dust is thought to increase dust light-scattering efficiency, cloud droplet activation, and nutrient solubility. However, the extent of African dust aging during long-range transport to the western Atlantic is poorly understood. Here, we explore African dust aging in wintertime samples collected from Barbados when dust is transported at lower altitudes. Ion chromatography (IC) analysis indicates that the mass concentrations of bulk nitrate, sulfate, and oxalate increase, relative to background conditions, when African dust reaches Barbados after transatlantic transport, indicating dust aging. However, aerosol mixing-state analysis from computer-controlled scanning electron microscopy with energy dispersive X-ray spectroscopy (CCSEM/EDX) indicates that approximately 67 % of dust particles are internally mixed with sea salt, while only about 26 % of dust particles contain no internally mixed components. SEM/EDX elemental mapping and time-of-flight secondary ion mass spectrometry (TOF-SIMS) reveals that within internally mixed dust and sea salt particles, only sea salt components contain signs of aging as indicated by the loss of chloride and acquisition of nitrate and/or sulfate. Our results suggest that chemical aging may only modestly increase the solubility of nutrients in African dust during long-range transport. Because most dust that we measured was internally mixed with sea salt, chemical aging is not necessarily required to increase the hygroscopicity of dust, at least in the lower boundary layer. Further, our findings have implications for understanding the release of halogens from sea salts, which may be enhanced in internally mixed dust and sea salt particles.

54 ENVIRONMENTAL SCIENCES

Imaging analysis of LDEF craters

Two small craters in Al from the Long Duration Exposure Facility (LDEF) experiment tray A11E00F (no. 74, 119 micron diameter and no. 31, 158 micron diameter) were analyzed using Auger electron spectroscopy (AES), time-of-flight secondary ion mass spectroscopy (TOF-SIMS), low voltage scanning electron microscopy (LVSEM), and SEM energy dispersive spectroscopy (EDS). High resolution images and sensitive elemental and molecular analysis were obtained with this combined approach. The result of these analyses are presented.

Radicatidibrozolo, F.

Image and compositional characteristics of the LDEF Big Guy impact crater

A 5.2 mm crater in Al-metal represents the largest found on LDEF. We have examined this crater by field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS) and time-of-flight/secondary ion mass spectroscopy (TOF-SIMS) in order to determine if there is any evidence of impactor residue. Droplet and dome-shaped columns, along with flow features, are evidence of melting. EDS from the crater cavity and rim show Mg, C, O and variable amounts of Si, in addition to Al. No evidence for a chondritic impactor was found, and it hypothesized that the crater may be the result of impact with space debris.

Bunch, T. E.

Looking for Fossil Bacteria in Martian Materials

The rationale for looking for prokaryote fossils in Martian materials is based on our present understanding of the environmental evolution of that planet in comparison to the history of the terrestrial environments and the development and evolution of life on Earth. On Earth we have clear, albeit indirect, evidence of life in 3.8 b.y.-old rocks from Greenland and the first morphological fossils in 3.3-3.5 b.y.-old cherts from South Africa and Australia. In comparison, Mars, being smaller, probably cooled down after initial aggregation faster than the Earth. Consequently, there could have been liquid water on its surface earlier than on Earth. With a similar exogenous and endogenous input of organics and life-sustaining nutrients as is proposed for the Earth, life could have arisen on that planet, possibly slightly earlier dm it did on Earth. Whereas on Earth liquid water has remained at the surface of the planet since about 4.4 b.y. (with some possible interregnums caused by planet-sterilising impacts before 3.8. b.y. and perhaps a number of periods of a totally frozen Earth, this was not the case with Mars. Although it is not known exactly when surficial water disappeared from the surface, there would have been sufficient time for life to have developed into something similar to the terrestrial prokaryote stage. However, given the earlier environmental deterioration, it is unlikely that it evolved into the eukaryote stage and even evolution of oxygenic photosynthesis may not have been reached. Thus, the impetus of research is on single celled life simnilar to prokaryotes. We are investigating a number of methods of trace element analysis with respect to the Early Archaean microbial fossils. Preliminary neutron activation analysis of carbonaceous layers in the Early Archaean cherts from South Africa and Australia shows some partitioning of elements such as As, Sb, Cr with an especial enrichment of lanthanides in a carbonaceous-rich banded iron sediment . More significantly, preliminary TOF-SIMS investigations of organics in the cherts reveals the presence of a biomarker, which appears to be a derivative of bacterial polymer, in the carbonaceous parts of the rocks. We conclude that a combination of morphological, isotope and biogeochemical methods can be used to successfully identify signs of life in terrestrial material, and that these methods will be useful in searching for signs of life in extraterrestrial materials.

Westall, F.

Sub-Micrometer Scale Minor Element Mapping in Interplanetary Dust Particles: A Test for Stratospheric Contamination

Combined X-ray microprobe (XRM), energy dispersive x-ray fluorescence using a Transmission Electron Microscope (TEM), and electron microprobe measurements have determined that the average bulk chemical composition of the interplanetary dust particles (IDPs) collected from the Earth s stratosphere is enriched relative to the CI meteorite composition by a factor of 2 to 4 for carbon and for the moderately volatile elements Na, K, P, Mn, Cu, Zn, Ga, Ge, and Se, and enriched to approximately 30 times CI for Br. However, Jessberger et al., who have reported similar bulk enrichments using Proton Induced X-ray Emission (PIXE), attribute the enrichments to contamination by meteor-derived atmospheric aerosols during the several weeks these IDPs reside in the Earth s atmosphere prior to collection. Using scanning Auger spectroscopy, a very sensitive surface analysis technique, Mackinnon and Mogk have observed S contamination on the surface of IDPs, presumably due to the accretion of sulfate aerosols during stratospheric residence. But the S-rich layer they detected was so thin (approximately 100 angstroms thick) that the total amount of S on the surface was too small to significantly perturb the bulk S-content of a chondritic IDP. Stephan et al. provide support for the contamination hypothesis by reporting the enrichment of Br on the edges of the IDPs using Time-of-Flight Secondary-Ion Mass-Spectrometry (TOFSIMS), but TOF-SIMS is notorious for producing false edge-effects, particularly on irregularly-shaped samples like IDPs. Sutton et al. mapped the spatial distribution of Fe, Ni, Zn, Br, and Sr, at the approximately 2 m scale, in four IDPs using element-specific x-ray fluorescence (XRF) computed microtomography. They found the moderately volatile elements Zn and Br, although spatially inhomogeneous, were not concentrated on the surface of any of the IDPs they examined, suggesting that the Zn and the Br enrichments in the IDPs are not due to contamination during stratospheric residence.

Flynn, G. J.

Teflon FEP Analyzed After Retrieval From the Hubble Space Telescope

During the Hubble Space Telescope (HST) Second Servicing Mission, 6.8 years after the telescope was deployed in low Earth orbit, degradation of unsupported Teflon FEP (DuPont; fluorinated ethylene propylene), used as the outer layer of the multilayer insulation (MLI) blankets, was evident as large cracks on the telescope light shield. A sample of the degraded outer layer (see the photograph) was retrieved during the second servicing mission and returned to Earth for ground testing and evaluation. Also retrieved was a Teflon FEP radiator surface from a cryogen vent cover that was exposed to the space environment on the aft bulkhead of the HST. NASA Goddard Space Flight Center directed the efforts of the Hubble Space Telescope MLI Failure Review Board, whose goals included determining the FEP degradation mechanisms. As part of the investigations into the degradation mechanisms, specimens retrieved from the first and second HST servicing missions, 3.6 and 6.8 years after launch, respectively, were characterized through exhaustive mechanical, optical, and chemical testing. Testing led by Goddard included scanning electron microscopy, optical microscopy, tensile testing, solar absorptance measurements, time-of-flight secondary ion mass spectroscopy (TOF-SIMS), Fourier transform infrared microscopy (m-FTIR), attenuated total reflectance infrared microscopy (ATR/FTIR), and x-ray diffraction (XRD). The NASA Lewis Research Center contributed significantly to the analysis of the retrieved HST materials by leading efforts and providing results of bend testing, surface microhardness measurements, x-ray photoelectron spectroscopy, solid-state nuclear magnetic resonance spectroscopy, and density measurements. Other testing was conducted by Nano Instruments, Inc., and the University of Akron.

Dever, Joyce A.

Oxidation of SiC/BN/SiC Composites in Reduced Oxygen Partial Pressures

SiC fiber-reinforced SiC composites with a BN interphase are proposed for use as leading edge structures of hypersonic vehicles. The durability of these materials under hypersonic flight conditions is therefore of interest. Thermogravimetric analysis was used to characterize the oxidation kinetics of both the constituent fibers and composite coupons at four temperatures: 816, 1149, 1343, and 1538 C (1500, 2100, 2450, and 2800 F) and in oxygen partial pressures between 5% and 0.1% (balance argon) at 1 atm total pressure. One edge of the coupons was ground off so the effects of oxygen ingress into the composite could be monitored by post-test SEM and EDS. Additional characterization of the oxidation products was conducted by XPS and TOF-SIMS. Under most conditions, the BN oxidized rapidly, leading to the formation of borosilicate glass. Rapid initial oxidation followed by volatilization of boria lead to protective oxide formation and further oxidation was slow. At 1538C in 5% oxygen, both the fibers and coupons exhibited borosilicate glass formation and bubbling. At 1538C in 0.1% oxygen, active oxidation of both the fibers and the composites was observed leading to rapid SiC degradation. BN oxidation at 1538C in 0.1% oxygen was not significant.

Opila, Elizabeth J.

Three Dimensional Structures of Particles Recovered from the Asteroid Itokawa by the Hayabusa Mission and a Role of X-Ray Microtomography in the Preliminary Examination

Particles of regolith on S-type Asteroid 25143 Itokawa were successfully recovered by the Hayabusa mission of JAXA (Japan Aerospace Exploration Agency). Near-infrared spectral study of Itokawa s surface indicates that these particles are materials similar to LL5 or LL6 chondrites. High-resolution images of Itokawa's surface suggest that they may be breccias and some impact products. At least more than 1500 particles were identified as Itokawa origin at curation facility of JAXA. Preliminary analysis with SEM/EDX at the curation facility shows that they are roughly similar to LL chondrites. Although most of them are less than 10 micron in size, some larger particles of about 100 micron or larger were also identified. A part of the sample (probably several tens particles) will be selected by Hayabusa sample curation team, and sequential examination will start from January 2011 by Hayabusa Asteroidal Sample Preliminary Examination Team (HASPET). In mainstream of the analytical flow, each particle will be examined by microtomography, XRD and XRF first as nondestructive analyses, and then the particle will be cut by an ultra-microtome and examined by TEM, SEM, EPMA, SIMS, PEEM/XANES, and TOF-SIMS sequentially. Three-dimensional structures of Itokawa particles will be obtained by microtomography sub-team of HASPET. The results together with XRD and XRF will be used for design of later destructive analyses, such as determination of cutting direction and depth, to obtain as much information as possible from small particles. Scientific results and a role of the microtomography in the preliminary examination will be presented.

Tsuchiyama, A.

Development of Genesis Solar Wind Sample Cleanliness Assessment: Initial Report on Sample 60341 Optical Imagery and Elemental Mapping

Since 2005 the Genesis science team has experimented with techniques for removing the contaminant particles and films from the collection surface of the Genesis fragments. A subset of ~40 samples have been designated as "cleaning matrix" samples. These are small samples to which various cleaning approaches are applied and then cleanliness is assessed optically, by TRXRF, SEM, ToF-SIMS, XPS, ellipsometry or other means [1-9]. Most of these sam-ples remain available for allocation, with cleanliness assessment data. This assessment allows evaluation of various cleaning techniques and handling or analytical effects. Cleaning techniques investigated by the Genesis community include acid/base etching, acetate replica peels, ion beam, and CO2 snow jet cleaning [10-16]. JSC provides surface cleaning using UV ozone exposure and ultra-pure water (UPW) [17-20]. The UPW rinse is commonly used to clean samples for handling debris between processing by different researchers. Optical microscopic images of the sample taken before and after UPW cleaning show what has been added or removed during the cleaning process.

Gonzalez, C. P.

Genesis Solar Wind Collector Cleaning Assessment: Update on 60336 Sample Case Study

To maximize the scientific return of Genesis Solar Wind return mission it is necessary to characterize and remove a crash-derived particle and thin film surface contamination. A small subset of Genesis mission collector fragments are being subjected to extensive study via various techniques. Here we present an update on the sample 60336, a Czochralski silicon (Si-CZ) based wafer from the bulk array (B/C). This sample has undergone multiple cleaning steps (see the table below): UPW spin wash, aggressive chemical cleanings (including aqua regia, hot xylene and RCA1), as well as optical and chemical (EDS, ToF-SIMS) imaging. Contamination appeared on the surface of 60336 after the initial 2007 UPW cleaning. Aqua regia and hot xylene treatment (8/13/2013) did little to remove contaminants. The sample was UPW cleaned for the third time and imaged (9/16/13). The UPW removed the dark stains that were visible on the sample. However, some features, like "the Flounder" (a large, 100 micron feature in Fig. 1b) appeared largely intact, resisting all previous cleaning efforts. These features were likely from mobilized adhesive, derived from the Post-It notes used to stabilize samples for transport from Utah after the hard landing. To remove this contamination, an RCA step 1 organic cleaning (RCA1) was employed. Although we are still uncertain on the nature of the Flounder and why it is resistant to UPW and aqua regia/hot xylene treatment, we have found RCA1 to be suitable for its removal. It is likely that the glue from sticky pads used during collector recovery may have been a source for resistant organic contamination [9]; however [8] shows that UPW reaction with crash-derived organic contamination does not make particle removal more difficult.

Goreva, Y. S.

Direct Analysis of Early Solar System Aqueous Fluids

We lack fundamental information on early solar system aqueous fluids. Fluid inclusions are present in carbonates, sulfides and halides in astro materials, whose characterization is finally becoming feasible. The ordinary chondrite regolith breccias Monahans 1998 (H5) and Zag (H3-6)contain fluid inclusion-bearing halite (NaCl) crystals dated at~4.5 billion years old. Freezing studies to measure the eutectic temperature demonstrated that the brines likely contain divalent cations(Ca, Mg, Fe). Halite is effective at preservation (at least 250 MY) of organic phases and structures. Thus, compositional data on fluid inclusions in halite will reveal unique information on the origin and activity of aqueous fluids in the early solar system, and interactions with organics. To measure fluid compositions from individual fluid inclusions we performed TOF-SIMS depth profiling a tultra-high vacuum at ~110 Kusing a 30 kVBi+analysis ion beam and a1 kVO2+sputtering ion beam. Halite fluid inclusion FI1 contains H2O, K,Na,Cl and NaCl•2H2O.FI2 contains H2O, K, Na, Cl, Al, Fe,Ca,NaCl•2H2O and C-N-O-H species originating from organic molecules. Mass overlap with NaOH species prevented definitive identification of Cain FI1.

M. E Zolensky

Surface heterogeneity propagation and homogenization for pouch cell-scale Li metal anodes

Li metal anode is a promising candidate for next-generation energy storage systems and is widely explored in Li-ion and solid-state batteries. Despite its potential, Li metal anodes face instabilities during long-term cycling, especially when paired with NMC or sulfur-based cathodes, where Li is cycled at high capacities of 6-8 mAh/cm2, equivalent to a thickness of 30-40 µm. During such extensive utilization, degradation mechanisms such as excessive solid electrolyte interphase (SEI), dendrites, and dead Li emerge, and ultimately lead to sudden failure and reduced cycle life. The origin of the degradation mechanisms stem from surface heterogeneities introduced during Li foil manufacturing and storage [1, 2]. As cycling progresses, the local heterogeneities propagate, resulting in uneven Li utilization and degradation-prone regions across the electrode [3], which consequently induce performance variations at the cell level. This heterogeneity propagation is particularly pronounced in large-format pouch cells in practical applications, where the surface effects are magnified. Without a clear understanding of the multi-scale heterogeneities and the development of surface homogenization methods, the performance consistency will be compromised, hindering the commercialization of Li metal batteries. In this presentation, we investigate the evolution of surface heterogeneity propagation on commercially available Li foils. We discover that inhomogeneous Li utilization appears as early as the first half-cycle of formation, manifesting as localized clusters and pits. In pouch cell configurations, these features exhibit areal density variations across the electrode on a scale of millimeters. To improve Li utilization homogeneity, a scalable mechanical brushing method is introduced to remove the chemically heterogeneous surface passivation layer. Furtherore, the influence of utilization homogeneity on cell-to-cell consistency is evaluated using 32 Li-NMC811 pouch cells divided into as-received and brushed Li groups. On the brushed Li, clusters and pits are no longer observable, and the cells exhibit significantly improved consistency in discharge capacity trajectories and cycle lifetime. Overall, this study highlights the role of Li surface utilization homogeneity on long-term cycling performance. Our research provides a pathway for improving large-area electrode uniformity and establishing evaluation methods for cell-to-cell consistency, both are key steps toward the commercialization of Li metal batteries and beyond. [1] Otto, Svenja-K., et al. "In-depth characterization of lithium-metal surfaces with XPS and ToF-SIMS: toward better understanding of the passivation layer." Chemistry of Materials 33.3 (2021): 859-867. [2] Hatzell, Kelsey, et al. "Aligning lithium metal battery research and development across academia and industry." Joule (2024). [3] Kim, Sangwook, et al. "Calendar life of lithium metal batteries: Accelerated aging and failure analysis." Energy Storage Materials 65 (2024): 103147.

25 - ENERGY STORAGE

Enhancing microsegregation during rapid directional solidification through ternary microalloying

The nano-cellular dendritic microstructure formed during rapid directional solidification in powder bed fusion additive manufacturing creates unique properties such as simultaneous improvement in strength and ductility. However, process control of microsegregation features remains challenging due to low sensitivity of critical solidification mechanisms to process parameters. This study leverages microalloying to achieve large changes in dendrite composition, microstructure, and interdendritic zone width during laser powder bed fusion without modifying process parameters. CALPHAD simulations predict that the addition of Zr significantly steepens the solidus line of the dilute Cu-Cr alloy system, leading to enhanced Cr rejection into the melt and greater than 95% reduction in solubility of Cr in the solidified Cu matrix. Experimental validation using time-of-flight secondary ion mass spectrometry and Kelvin probe force microscopy reveals that the ternary alloy containing 0.01 wt% Zr exhibited wider interdendritic regions compared to the binary, a significantly higher number of Cr-rich particles within interdendritic regions, near-complete ejection of oxygen impurities from the matrix, and greater nanoscale work function contrast. These features indicate more aggressive Cr segregation in the presence of Zr and a purer Cu matrix and provide a potentially robust method for engineering the nano-cellular dendritic solidification microstructure.

CALPHAD