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Terahertz response of monolayer and few-layer WTe2 at the nanoscale

Abstract Tungsten ditelluride (WTe 2 ) is an atomically layered transition metal dichalcogenide whose physical properties change systematically from monolayer to bilayer and few-layer versions. In this report, we use apertureless scattering-type near-field optical microscopy operating at Terahertz (THz) frequencies and cryogenic temperatures to study the distinct THz range electromagnetic responses of mono-, bi- and trilayer WTe 2 in the same multi-terraced micro-crystal. THz nano-images of monolayer terraces uncovered weakly insulating behavior that is consistent with transport measurements. The near-field signal on bilayer regions shows moderate metallicity with negligible temperature dependence. Subdiffractional THz imaging data together with theoretical calculations involving thermally activated carriers favor the semimetal scenario with $$\Delta \approx -10\,{{{\rm{meV}}}}$$ Δ ≈ − 10 meV over the semiconductor scenario for bilayer WTe 2 . Also, we observed clear metallic behavior of the near-field signal on trilayer regions. Our data are consistent with the existence of surface plasmon polaritons in the THz range confined to trilayer terraces in our specimens. Finally, data for microcrystals up to 12 layers thick reveal how the response of a few-layer WTe 2 asymptotically approaches the bulk limit.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

High-throughput, in situ imaging of multi-layer powder-blown directed energy deposition with angled nozzle

Laser metal additive manufacturing (AM) has become an increasingly popular technology due to its flexibility in geometry and materials. As one of the commercialized additive processes, powder-blown directed energy deposition (DED) has been used in multiple industries such as aerospace, automotive, medical device, etc. However, a lack of fundamental understanding remains for this process, and many opportunities for alloy development and implementation can be identified. A high-throughput, in situ DED system capable of multi-layer builds that can address these issues is presented here. In this work, implications of layer heights and energy density are investigated through an extensive process parameter sweep, showcasing the power of a high-throughput setup while also discussing multi-layer interactions.

47 OTHER INSTRUMENTATION↗

Luminescence and Thermal Imaging Applied to Half-Cut-Cell and Emitter-Wrap-Through-Cell Modules

Imaging techniques provide spatial details and visualization of module defects and degradation mechanisms that affect energy conversion efficiency and performance. We apply photoluminescence, electroluminescence, and dark lock-in thermography imaging techniques to evaluate new modules in their initial state and after applying stresses of damp heat, light-induced-degradation regeneration parameters, thermal cycling, and humidity-freeze cycles. One module uses emitter-wrap-through cells with back contacts connected to a metal-foil backplane, and the other is composed of half-cut cells. Imaging shows examples on non-uniform degradation and damage such as cells that degrade and recover under the applied conditions, cells with cracks and handling damage, and cells with increasing series resistance.

degradation↗

RF Device for Acquiring Images of the Human Body

A safe, non-invasive method for forming images through clothing of large groups of people, in order to search for concealed weapons either made of metal or not, has been developed. A millimeter wavelength scanner designed in a unique, ring-shaped configuration can obtain a full 360 image of the body with a resolution of less than a millimeter in only a few seconds. Millimeter waves readily penetrate normal clothing, but are highly reflected by the human body and concealed objects. Millimeter wave signals are nonionizing and are harmless to human tissues when used at low power levels. The imager (see figure) consists of a thin base that supports a small-diameter vertical post about 7 ft (=2.13 m) tall. Attached to the post is a square-shaped ring 2 in. (=5 cm) wide and 3 ft (=91 cm) on a side. The ring is oriented horizontally, and is supported halfway along one side by a connection to a linear bearing on the vertical post. A planar RF circuit board is mounted to the inside of each side of the ring. Each circuit board contains an array of 30 receivers, one transmitter, and digitization electronics. Each array element has a printed-circuit patch antenna coupled to a pair of mixers by a 90 coupler. The mixers receive a reference local oscillator signal to a subharmonic of the transmitter frequency. A single local oscillator line feeds all 30 receivers on the board. The resulting MHz IF signals are amplified and carried to the edge of the board where they are demodulated and digitized. The transmitted signal is derived from the local oscillator at a frequency offset determined by a crystal oscillator. One antenna centrally located on each side of the square ring provides the source illumination power. The total transmitted power is less than 100 mW, resulting in an exposure level that is completely safe to humans. The output signals from all four circuit boards are fed via serial connection to a data processing computer. The computer processes the approximately 1-MB data set into a three-dimensional image in a matter of seconds. The innovation is to configure the receiver array in a ring topology surrounding the scanned object. The ring is then scanned vertically to cover the necessary two-dimensional surface. This fabrication of the ring is made possible by using planar antenna and circuit technology. A planar circuit board serves as a medium for both antennas and signal processing components. Using this technique, parts counts are kept low, and the cost per element is a small fraction of a waveguide-based system.

Gaier, Todd C.↗

Multiscale dynamic experiments on fiber-reinforced composites with damage assessment using high-speed synchrotron X-ray phase-contrast imaging

We report fiber-reinforced composites (FRCs) have been widely used as protection materials to replace heavier metals. However, predictive capabilities for the impact-induced failure of FRCs have not been well-developed. In this work, we introduced an integrated technique to visualize the dynamic failure of FRCs, with the modified Kolsky bar loading and the high-speed synchrotron X-ray phase-contrast imaging (PCI). We summarize our experimental studies across the FRCs’ structural levels by using this integrated technique, including single-fiber tensile experiments, fiber/matrix debonding experiments, and single-edge notched bending experiments on composite laminates. It is revealed that the high-speed synchrotron X-ray PCI technique possesses sufficient spatial resolution to identify the failure behavior of a single fiber in the 10-μm scale level, as well as temporal resolution to identify the time sequence of internal dynamic damage evolution. The technique can penetrate through the opaque composite sample and provide real-time visualization of small-scale damaging mechanisms such as the embedded fiber’s sliding in the matrix and the fiber’s transverse debonding with the matrix. At an expanding scale, the technique can identify the crack initiation and track the cracking behavior inside a single ply or between different plies of a composite laminate. High-speed visualization inside the material by this integrated technique provides critical deformation and failure information to develop physical understanding of the damage inside composites under impact.

47 OTHER INSTRUMENTATION↗

In situ synchrotron X-ray imaging and mechanical properties characterization of additively manufactured high-entropy alloy composites

Laser beam directed energy deposition has become an increasingly popular advanced manufacturing technique for materials discovery as a result of the in situ alloying capability. In this study, we leverage an additive manufacturing enabled high throughput materials discovery approach to explore the composition space of a graded W x (CoCrFeMnNi) 100–x sample spanning 0 ≤ x ≤ 21 at%. In addition to microstructural and mechanical characterization, synchrotron high speed x-ray computer aided tomography was conducted on a W 20 (CoCrFeMnNi) 80 composition to visualize melting dynamics, powder-laser interactions, and remelting effects of previously consolidated material. Results reveal the formation of the Fe 7 W 6 intermetallic phase at W concentrations> 6 at%, despite the high configurational entropy. Unincorporated W particles also occurred at W concentrations> 10 at% accompanied by a dissolution band of Fe 7 W 6 at the W/matrix interface and hardness values greater than 400 HV. In this work, the primary strengthening mechanism is attributed to the reinforcement of the Fe 7 W 6 and W phases as a metal matrix composite. The in situ high speed x-ray imaging during remelting showed that an additional laser pass did not promote further mixing of the Fe 7 W 6 or W phases suggesting that, despite the dissolution of the W into the Fe 7 W 6 phase being thermodynamically favored, it is kinetically limited by the thickness/diffusivity of the intermetallic phase, and the rapid solidification of the laser-based process.

36 MATERIALS SCIENCE↗

The Ionization and Metallicity of the Intervening O VI Absorber at z=0.1212 in the Spectrum of H1821+643

We use high-resolution UV (ultraviolet) spectra of the radio-quiet QSO (quasi-stellar object) H1821+643 (z(sub em) = 0.297), obtained with the Space Telescope Imaging Spectrograph (STIS) and the Far Ultraviolet Spectroscopic Explorer (FUSE), to study the ionization and metallicity of an intervening O VI absorption line system at z(sub abs) = 0.1212. This absorber has the following notable properties: (1) Several galaxies are close to the sight line at the absorber redshift, including an actively star-forming galaxy at a projected distance of 144 h(sub 75)(exp -1) kpc. (2) There is a complex cluster of H I Ly(alpha) absorption lines near the O VI redshift, including at least five components spread over a velocity range of approximately 700 km s(exp -1). (3) The strongest Ly(alpha) line in the cluster appears to be composed of a mildly saturated component with a typical b-value blended with a remarkably broad component with b approximately equals 85 km s(exp -1). (4) The O VI absorption is not aligned with the strongest (saturated) H I absorption, but instead is well-aligned with the very broad component. (5) The only detected species (at the 4(sigma) level) are O VI and H I despite coverage of strong transitions of abundant elements (e.g., C II, C III, and C IV). Based on these constraints, we find that the absorption line properties can be produced in collisionally ionized gas with 10(exp 5.3) is equal to or less than T is equal to or less than 10(exp 5.6) K and -1.8 is equal to or less than [O/H] is equal to or less than -0.6. However, we find that photoionization is also viable if the pathlength l through the absorbing gas is long enough; simple photoionization models require 85 is equal to or less than l is equal to or less than 1900 kpc and -1.1 is equal to or less than [O/H] is equal to or less than -0.3. We briefly discuss how observations of X-ray absorption lines due to O VII and O VIII could be used, in principle, to break the ionization mechanism degeneracy, and we conclude with some comments regarding the nature of O VI absorbers.

Tripp, Todd M.↗

The safety of magnetic resonance imaging contrast agents

Gadolinium-based contrast agents are increasingly used in clinical practice. While these pharmaceuticals are verified causal agents in nephrogenic systemic fibrosis, there is a growing body of literature supporting their role as causal agents in symptoms associated with gadolinium exposure after intravenous use and encephalopathy following intrathecal administration. Gadolinium-based contrast agents are multidentate organic ligands that strongly bind the metal ion to reduce the toxicity of the metal. The notion that cationic gadolinium dissociates from these chelates and causes the disease is prevalent among patients and providers. We hypothesize that non-ligand-bound (soluble) gadolinium will be exceedingly low in patients. Soluble, ionic gadolinium is not likely to be the initial step in mediating any disease. The Kidney Institute of New Mexico was the first to identify gadolinium-rich nanoparticles in skin and kidney tissues from magnetic resonance imaging contrast agents in rodents. In 2023, they found similar nanoparticles in the kidney cells of humans with normal renal function, likely from contrast agents. We suspect these nanoparticles are the mediators of chronic toxicity from magnetic resonance imaging contrast agents. This article explores associations between gadolinium contrast and adverse health outcomes supported by clinical reports and rodent models.

59 BASIC BIOLOGICAL SCIENCES↗

COOL-LAMPS. II. Characterizing the Size and Star Formation History of a Bright Strongly Lensed Early-type Galaxy at Redshift 1.02

We present COOL J1323+0343, an early-type galaxy at z = 1.0153 ± 0.0006, strongly lensed by a cluster of galaxies at z = 0.353 ± 0.001. This object was originally imaged by DECaLS and noted as a gravitational lens by COOL-LAMPS, a collaboration initiated to find strong-lensing systems in recent public optical imaging data, and confirmed with follow-up data. With ground-based grzH imaging and optical spectroscopy from the Las Campanas Observatory and the Nordic Optical Telescope, we derive a stellar mass, metallicity, and star formation history from stellar-population synthesis modeling. The lens modeling implies a total magnification, summed over the three images in the arc, of μ ~ 113. The stellar mass in the source plane is M * ~ 10.64 M ⊙ and the 1σ upper limit on the star formation rate (SFR) in the source plane is SFR ~ 3.75 × 10 -2 M ⊙ yr -1 (log sSFR = -12.1 yr -1 ) in the youngest two age bins (0–100 Myr), closest to the epoch of observation. Our measurements place COOL J1323+0343 below the characteristic mass of the stellar mass function, making it an especially compelling target that could help clarify how intermediate-mass quiescent galaxies evolve. We reconstruct COOL J1323+0343 in the source plane and fit its light profile. This object is below the expected size evolution of an early-type galaxy at this mass with an effective radius r e ~ 0.5 kpc. This extraordinarily magnified and bright lensed early-type galaxy offers an exciting opportunity to study the morphology and star formation history of an intermediate-mass early-type galaxy in detail at z ~ 1.

79 ASTRONOMY AND ASTROPHYSICS↗

Direct Observation of Electron Beam-Induced Phase Transition in MgCrMnO 4

Irreversible structural transformation in intercalation-type cathode materials, which has been frequently observed, has been perceived as a principal cause of capacity fading and voltage decay in (uni) multivalent batteries. Herein, we explored the electron beam-induced spinel to defective rocksalt phase transitions in MgCrMnO 4 , a potential multivalent cation intercalation cathode, using atomic-resolution imaging and spectroscopy in an aberration-corrected scanning transmission electron microscope. This dynamic electron beam irradiation study of specific structural transformations provides an atomistic understanding of the structural evolution observed in transition-metal oxide spinels during electrochemical cycling using multivalent cations, such as Mg 2+ . By combining an imaging study with first-principles modeling, we demonstrate that the mechanism of the spinel to defective rocksalt transformation in MgCrMnO 4 nanostructures is enabled by the presence of oxygen vacancies and is, therefore, very similar to that observed in transition-metal oxide spinels upon Li intercalation.

36 MATERIALS SCIENCE↗

A Transmission Electron Microscopy Study of a Refractory Metal Grain from a Calcium-Aluminum-Rich Inclusion in the Leoville CV3 Chondrite

Introduction: Calcium-aluminum-rich inclusions (CAIs) are an important component of chondritic meteorites. They can contain materials that are thermodynamically predicted and isotopically age dated to be among the first-formed solids in our solar system [1-5]. Observed in some CAIs are micron to sub-micron sized inclusions rich in Fe, Ni, and high-Z elements such as Pt, Os, Ir and W, in the form of refractory metal nuggets (RMNs), fremdlinges, and ‘nugget like objects’ (NLOs) [1,6]. Refractory siderophile elements such as Os, Ir and Ru are thermodynamically predicted to condense at temperatures well in excess of the major CAI phases such as melilite, perovskite, spinel and hibonite [2,7-9]. These refractory metal inclusions in CAIs can therefore serve as probes into the thermodynamic landscape of the early solar protoplanetary disk. Here we report on a refractory grain identified in a CAI of the Leoville CV3 chondrite. This work is part of an ongoing effort to gain insight into the thermochemistry of the early solar system through systematic analyses of the structure and chemistry of various components in CAIs [10-13]. Sample and Analytical Techniques: A fluffy type A CAI (Fig. 1A) was identified in a section of the Leoville, CV3 chondrite (Center for Meteorite Studies, Arizona State University collection, #821_C_3) using a JOEL-JXA 8530F electron microprobe at Arizona State University. Backscattered electron (BSE) imaging and energy-dispersive X-ray spectroscopy (EDS) were used to identify refractory metal grains in the CAI using a Thermo Fisher (formerly FEI) Helios NanoLab 660 G3 focused-ion-beam scanning-electron microscope (FIBSEM) located at the Kuiper Materials Imaging and Characterization Facility (KMICF) at the Lunar and Planetary Laboratory, University of Arizona. The FIB is equipped with an EDAX EDS system. We selected one of the larger (micron-sized) refractory metal grains, designated as ‘Spud’ (Fig. 1B) for further analysis. ‘Spud’ was extracted and thinned to electron transparency (<100 nm) using the FIB-SEM located in KMICF, following methods described by [14- 15]. The FIB section was analyzed using a 200 keV Hitachi HF5000 scanning transmission electron microscope (S/TEM) located at KMICF. The HF5000 is equipped with cold-field emission gun, 3rd-order spherical aberration corrector for STEM imaging, and an Oxford Instruments X-Max N 100 TLE energydispersive spectroscopy (EDS) system with dual 100 mm2 windowless silicon-drift detectors (Ω = 2.0 sr). Selected-area electron-diffraction (SAED) patterns were acquired to aid in determination of crystallinity and phase. Results: The mineralogy, texture, and morphology of the CAI are consistent with that of a fluffy type A (FTA) CAI [16]. BSE imaging at high magnifications revealed grains with high contrast, indicative of compositions rich in elements of higher atomic number relative to surrounding material. These high-Z grains have sizes that range from ∼250 nm to 4 µm. EDS analyses confirm that the bright grains are metal-rich inclusions. A minor fraction of the grains are composed of only Fe and Ni, but the majority (∼60%) of the identified inclusions also contained various refractory siderophiles including Os, Ru, Zr, Ir and Mo. EDS analysis on the FIB-SEM of Spud shows that it contains Fe, Ni, Mo and Ru. High-angle annular dark-field (HAAFD) imaging and EDS mapping in the TEM (Fig. 2) show that Spud occurs in melilite (Ca1.9Al1.99Si1.06O7). Spud contains a subhedral to anhedral morphology and is compositionally heterogenous (polyphasic, Fig. 2). Local spatial correlation occurs among Fe, Ni, and Pt, and also among Os, Ru, and Mo. SAED patterns show that the Fe-Ni-Pt, Fe-Os-Mo-Ru and Fe-Pt regions are crystalline. Discussion: CAIs can contain various types of inclusions rich in Fe, Ni and refractory siderophiles such as Os, Ru, W and Pt [1]. RMNs are micron-sized, single phase alloy grains and can contain Os, Ir, Ru and Rh [1,7,17]. NLOs are also micron-sized inclusions, but contain two phases, a refractory metal, and an oxide [6]. Fremdlinge are the largest of such inclusions (tens of microns in size) and are complex aggregates of Fe-Ni alloy, silicates, oxides, and sulfides [1,17]. While the size of Spud matches previous descriptions of RMNs and NLOs, Spud is neither a single-phase alloy like RMNs, nor does it contain one metal phase and one oxide like NLOs. Spud does not match the above described categories of refractory metal inclusions. The presence of refractory siderophiles such as Mo, Os, Ru, and Pt suggests a high-temperature origin. Thermodynamic modelling by [7] indicates condensation temperatures of 1917 K, 1693 K, 1613 K and 1415 K for Os, Mo, Ru and Pt respectively. These models also show that following the initial condensation of a refractory metal, alloying of solutes such as Fe, Ni and W, occurs in levels proportional to their partial pressures in the surrounding gas. Such alloying occurs at temperatures above the condensation temperatures of common CAI phases such as melilite (1529 K), perovskite (1441 K), spinel (197 K) and forsterite (1354 K) [2]. The polyphasic nature of Spud could be the result of such high-temperature alloying, possibly shortly after the condensation of Mo and Ru at 1693 K and 1613 K respectively. That Spud occurs as an inclusion is consistent with it having formed prior to and at temperature above that of its host melilite in this FTA CAI, which is qualitatively consistent with such prior thermodynamic modeling. Further, the polyphasic nature of Spud is similar to refractory grains from a FTA CAI in the Northwest Africa (NWA) 8323, CV3 chondrite [11-13]. These data suggest that such refractory metal grains could have been widespread in the inner and early solar protoplanetary disk and represent some of the earliest formed solids to have condensed. Acknowledgments: Research and instrumentation supported by NASA grants #NNX12AL47G, #NNX15AJ22G and #80NSSC19K0509, and NSF grants #1531243 and #0619599. Fig 2. STEM data on ‘Spud’. HAADF Image (Top) False-color EDS Maps (Bottom) References: [1] MacPherson G. J. (2014) T. of Geochem. Vol I: Met. And Cosmochem. Processes, 139-179. [2] Lodders K. (2003) ApJ, 591, 1220-1247. [3] Ebel D. S. (2006) Met. & the Early S. Sys. II., 253- 277. [4] Amelin Y. (2002) Science, 297, 1678-1683. [5] Connelly J.N. et.al. (2012) Science, 338, 651-655. [6] Schwander D. et al. (2015) GCA, 18, 70-87. [7] Palme H. and Wlotzka F. (1976) EPSL, 33, 45-60. [8] Berg T. et al. (2009) ApJ, 702, 172-176. [9] Liffman K. et al. (2021) Icarus, 221, 89-105. [10] Zega T.J. et al. (2021) PSJ, 2, 115. [11] Ramprasad T. et al. (2020) LPSC LI, Abstract #2472. [12] Ramprasad T. et al. (2021) Microscopy & Microanalysis, S1, 2792-2794. [13] Ramprasad T. et al. (2021) 84th MetSoc, Abstract #6123. [14] Zega T.J. et al. (2007) MAPS, 42, 1373-1386. [15] Ramprasad T. et al. (2022) MAPS, in revision. [16] Grossman L. (1975), GCA, 39, 433-454. [17] El Goresy A. et al. (1978) LPSC IX, Abstract#1100

T. Ramprasad↗

Hyperspectral and Nanosecond Temporal Resolution Widefield Infrared Photothermal Heterodyne Imaging

Label-free, bond-selective imaging offers new opportunities for fundamental and applied studies in chemistry, biology, and materials science. Preventing its broader application to investigating spectrally congested specimens are issues related to low sensitivity as well as low spatial and temporal resolution. Here, we demonstrate a widefield, mid-infrared (MIR) photothermal imaging technique, called widefield Infrared Photothermal Heterodyne imaging (wIR-PHI), that massively parallelizes acquisition of MIR absorption data through use of a high-speed complementary metal-oxide-semiconductor camera. wIR-PHI possesses notable features that include: spatial resolution significantly below the MIR diffraction limit, hyperspectral imaging capabilities, high sensitivity, and ~100 ns temporal resolution. Here, the first two features are highlighted by hyperspectral imaging of proximally close poly(methyl methacrylate) (PMMA) and polystyrene (PS) nanoparticles where clear, bond-specific imaging of nanoparticles, separated by less than the MIR diffraction limit, is demonstrated. Sensitivity is highlighted by imaging individual PMMA and PS nanoparticles with radii between r = 97-556 nm. This leads to a current, peak absorption cross-section limit-of-detection of σ abs = 1.9× 10 –16 cm 2 . wIR-PHI's 100 ns temporal resolution is simultaneously demonstrated by observing the decay of photothermal contrast on individual nanoparticles on a ~200-6000 ns timescale. In whole, wIR-PHI’s dramatic increase in acquisition speed opens opportunities for future MIR kinetic imaging and spectroscopic studies of important chemical, biological, and material processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Applying Multimodal Mass Spectrometry to Image Tumors Undergoing Ferroptosis Following In Vivo Treatment with a Ferroptosis Inducer

Epithelial ovarian cancer (EOC) is the most common form of ovarian cancer. The poor prognosis generally associated with this disease has led to the search for improved therapies such as ferroptosis-inducing agents. Ferroptosis is a form of regulated cell death that is dependent on iron and is characterized by lipid peroxidation. Precise mapping of lipids and iron within tumors exposed to ferroptosis-inducing agents may provide insight into processes of ferroptosis in vivo and ultimately assist in the optimal deployment of ferroptosis inducers in cancer therapy. In this work, we present a method for combining matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) with secondary ion mass spectrometry (SIMS) to analyze changes in spatial lipidomics and metal composition, respectively, in ovarian tumors following exposure to a ferroptosis inducer. Tumors were obtained by injecting human ovarian cancer tumor-initiating cells into mice, followed by treatment with the ferroptosis inducer erastin. SIMS imaging detected iron accumulation in the tumor tissue, and sequential MALDI-MS imaging of the same tissue section displayed two chemically distinct regions of lipids. Additionally, one region was associated with the iron-rich area detected with SIMS, and the other region encompassed the remainder of the tissue section. Bulk lipidomics confirmed the lipid assignments putatively assigned from the MALDI-MS data. Overall, we demonstrate the ability of multimodal MSI to identify the spatial locations of iron and lipids in the same tissue section and associate these regions with clinical pathology.

60 APPLIED LIFE SCIENCES↗

Investigation of the Anisotropy of Y-Ba-Cu-O Thin Films With Photoemission Electron Microscopy

Understanding the anisotropy in the electrical properties of YBa2Cu3O7-δ (YBCO) is important for understanding the fundamental mechanism of superconductivity in unconventional superconductors. Additionally it is also essential for achieving uniform and controllable critical currents and resistances in YBCO Josephson junctions. Here, this study correlates work function measurements of different intrinsic regions on YBCO thin films, obtained through PhotoEmission Electron Microscopy (PEEM), with in plane tunneling data and helium ion imaging. YBCO thin films, 40 nm in thickness, were selectively irradiated with 300 keV helium using a Pelletron to investigate the effects of irradiation compared to unirradiated regions. Post-irradiation PEEM images revealed distinct contrasts between irradiated and non-irradiated regions, suggesting a metal-to-insulator transition. In non-irradiated areas, a domain pattern was detected, showing a 25 meV difference in work function, attributed to CuO and BaO rich surface regions. A similar domain structure was observed using high-resolution helium ion imaging; however, the helium ion beam can damage the YBCO, making PEEM a valuable non-destructive alternative. This work highlights the correlation between PEEM measurements and in-plane tunneling properties of YBCO, providing insights into material orientation and its impact on Josephson junction performance. Furthermore, it offers a non-destructive approach to understanding the anisotropy of cuprate materials, its superconducting properties, and the factors affecting Josephson junction performance.

Qu, Rochelle Y. [Univ. of California, Riverside, C↗

Atomic-scale Imaging of PGM-free Catalyst Active Sites by 30 keV 4D-STEM

Platinum group metal (PGM)-free catalysts have attracted a large amount of attention due to their potential for enabling low-cost, commercially viable hydrogen fuel cells and electrolyzers [1]. Degradation of cell performance remains a significant challenge, however, currently limiting implementation of devices that utilize PGM-free materials [2]. Controlling degradation in these materials requires a better understanding of the atomic structure of active sites, thought to be FeN4 structures within a graphitic carbon lattice, which would enable more accurate prediction of the associated degradation pathways. The exact structural arrangement of active sites in these materials is still debated since a range of structures have been computationally predicted and methods to directly validate these models are still needed [1,3-5].While scanning transmission electron microscopy (STEM) has provided initial glimpses into the nature of the proposed active sites, detailed evaluation of the structure of these sites is challenging since they involve defects, edges, and nitrogen dopants in the graphitic lattice, which are susceptible to beam damage [6,7]. Conventional STEM imaging and spectroscopy methods exacerbate this problem with dose-inefficiency or nonideal contrast characteristics for imaging light and heavy elements simultaneously. A method that minimizes damage while generating dose-efficient, easily-interpretable contrast for both light and heavy elements is therefore needed to facilitate imaging of sensitive active site atomic structure.Here, we demonstrate direct atomic-scale imaging of PGM-free catalyst active sites by low-voltage four-dimensional (4D)-STEM. To accomplish this, we pair a 30 keV aberration-corrected probe, which minimizes knock-on damage, with a fast pixelated detector that has optimal performance at low beam energies [8]. We show how this setup enables relatively simple center-of-mass (CoM) techniques [9,10] to produce images with an increased signal-to-noise ratio (SNR) and light-element contrast over conventional imaging modes, allowing the entire active site structure to be imaged at the atomic scale. Moreover, we show how electron ptychography [11,12] enables images with further improved characteristics to be obtained, for example by minimizing residual aberrations, which provides a more accurate structural representation. The increased understanding that these low-voltage 4D-STEM techniques will provide about the atomic structure of PGM-free active sites and their associated degradation pathways will facilitate rational design of next-generation materials, promoting development of low-cost hydrogen fuel cells, electrolyzers, and other energy conversion devices [13]. References:[1] U Martinez et al., Adv. Mater. 31 (2019), p. 1806545.[2] Y Shao et al., Adv. Mater. 31 (2019), p. 1807615.[3] J Kneebone et al., J. Phys. Chem. C 121, (2017), p.16283.[4] T Mineva et al., ACS Catal. 9 (2019), p. 9359.[5] J Li et al., Nat. Catal. 4 (2021), p. 10.[6] T Susi et al., ACS Nano 6 (2012), p. 8837.[7] P Zelenay and DJ Myers, US Department of Energy Hydrogen and Fuel Cells Program 2017 Annual Merit Review and Peer Evaluation Meeting, Washington, DC (2017).[8] H Ryll et al., J. Inst. 11 (2016), p. P04006.[9] K Müller et al., Nat. Commun. 5 (2014), p. 5653.[10] I Lazic et al., Ultramicroscopy 160 (2016), p. 265.[11] H Yang et al., Nat. Commun. 7 (2016), p. 12532.[12] Y Jiang et al., Nature 559 (2018), p. 343. [13] Research sponsored by the Hydrogen and Fuel Cell Technologies Office, Office of Energy Efficiency and Renewable Energy, US Department of Energy (DOE). Research was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility.

Zachman, Michael↗

Mid-infrared photodetection with 2D metal halide perovskites at ambient temperature

The detection of mid-infrared (MIR) light is technologically important for applications such as night vision, imaging, sensing, and thermal metrology. Traditional MIR photodetectors either require cryogenic cooling or have sophisticated device structures involving complex nanofabrication. Here, we conceive spectrally tunable MIR detection by using two-dimensional metal halide perovskites (2D-MHPs) as the critical building block. Leveraging the ultralow cross-plane thermal conductivity and strong temperature-dependent excitonic resonances of 2D-MHPs, we demonstrate ambient-temperature, all-optical detection of MIR light with sensitivity down to 1 nanowatt per square micrometer, using plastic substrates. Through the adoption of membrane-based structures and a photonic enhancement strategy unique to our all-optical detection modality, we further improved the sensitivity to sub–10 picowatt-per-square-micrometer levels. The detection covers the mid-wave infrared regime from 2 to 4.5 micrometers and extends to the long-wave infrared wavelength at 10.6 micrometers, with wavelength-independent sensitivity response. Our work opens a pathway to alternative types of solution-processable, long-wavelength thermal detectors for molecular sensing, environmental monitoring, and thermal imaging.

Li, Yanyan [Yale University, New Haven, CT (United↗

N-Type delta Doping of High-Purity Silicon Imaging Arrays

A process for n-type (electron-donor) delta doping has shown promise as a means of modifying back-illuminated image detectors made from n-doped high-purity silicon to enable them to detect high-energy photons (ultraviolet and x-rays) and low-energy charged particles (electrons and ions). This process is applicable to imaging detectors of several types, including charge-coupled devices, hybrid devices, and complementary metal oxide/semiconductor detector arrays. Delta doping is so named because its density-vs.-depth characteristic is reminiscent of the Dirac delta function (impulse function): the dopant is highly concentrated in a very thin layer. Preferably, the dopant is concentrated in one or at most two atomic layers in a crystal plane and, therefore, delta doping is also known as atomic-plane doping. The use of doping to enable detection of high-energy photons and low-energy particles was reported in several prior NASA Tech Briefs articles. As described in more detail in those articles, the main benefit afforded by delta doping of a back-illuminated silicon detector is to eliminate a "dead" layer at the back surface of the silicon wherein high-energy photons and low-energy particles are absorbed without detection. An additional benefit is that the delta-doped layer can serve as a back-side electrical contact. Delta doping of p-type silicon detectors is well established. The development of the present process addresses concerns specific to the delta doping of high-purity silicon detectors, which are typically n-type. The present process involves relatively low temperatures, is fully compatible with other processes used to fabricate the detectors, and does not entail interruption of those processes. Indeed, this process can be the last stage in the fabrication of an imaging detector that has, in all other respects, already been fully processed, including metallized. This process includes molecular-beam epitaxy (MBE) for deposition of three layers, including metallization. The success of the process depends on accurate temperature control, surface treatment, growth of high-quality crystalline silicon, and precise control of thicknesses of layers. MBE affords the necessary nanometer- scale control of the placement of atoms for delta doping. More specifically, the process consists of MBE deposition of a thin silicon buffer layer, the n-type delta doping layer, and a thin silicon cap layer. The n dopant selected for initial experiments was antimony, but other n dopants as (phosphorus or arsenic) could be used. All n-type dopants in silicon tend to surface-segregate during growth, leading to a broadened dopant-concentration- versus-depth profile. In order to keep the profile as narrow as possible, the substrate temperature is held below 300 C during deposition of the silicon cap layer onto the antimony delta layer. The deposition of silicon includes a silicon- surface-preparation step, involving H-termination, that enables the growth of high-quality crystalline silicon at the relatively low temperature with close to full electrical activation of donors in the surface layer.

Blacksberg, Jordana↗

Identification of a quasi-liquid phase at solid–liquid interface

Abstract An understanding of solid–liquid interfaces is of great importance for fundamental research as well as industrial applications. However, it has been very challenging to directly image solid–liquid interfaces with high resolution, thus their structure and properties are often unknown. Here, we report a quasi-liquid phase between metal (In, Sn) nanoparticle surfaces and an aqueous solution observed using liquid cell transmission electron microscopy. Our real-time high-resolution imaging reveals a thin layer of liquid-like materials at the interfaces with the frequent appearance of small In nanoclusters. Such a quasi-liquid phase serves as an intermediate for the mass transport from the metal nanoparticle to the liquid. Density functional theory-molecular dynamics simulations demonstrate that the positive charges of In ions greatly contribute to the stabilization of the quasi-liquid phase on the metal surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗