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At least 55 records · Page 3

Raman spectroscopic investigation of ianthinite [U$_2^{4+}$(UO$_2$)$_4$O$_6$(OH)$_4$(H$_2$O)$_4$]·$5$H$_2$O, a rare mixed-valence uranium oxide hydrate

Ianthinite ([[U$_2^{4+}$(UO$_2$)$_4$O$_6$(OH)$_4$(H$_2$O)$_4$]·$5$H$_2$O) is an exotic mineral that possesses U in both tetravalent and hexavalent oxidation states and is structurally related to the U 3 O 8 polymorphs, which are commonly encountered technogenic materials in the nuclear fuel cycle. Despite the similarities between U 3 O 8 and ianthinite, and the importance of ianthinite in U paragenesis, no Raman spectra have been reported for this mineral. Here, to gain a more complete understanding of how structural attributes of ianthinite give rise to observable spectroscopic features and how these may relate to important materials in the nuclear fuel cycle, we provide, for the first time, Raman spectra of ianthinite. Ianthinite readily oxidizes at ambient conditions, complicating analysis of phase-pure material. Several analytical methods are employed herein to decouple the Raman features of ianthinite from its alteration product(s). First, a simple difference spectrum is presented, then results of Raman spectroscopic mapping are employed, and finally, we use a novel processing and analysis method. Each analysis method provides different insight into structural features that are unique to ianthinite, in particular, features that are attributable to U(IV) in distorted octahedral coordination in both ianthinite and U 3 O 8 phases.

Spano, Tyler L. [Oak Ridge National Laboratory (OR↗

Rapid Oxidation of Uranium Steel Alloys: Combustion Synthesis

This project explored the use of combustion synthesis as a rapid, high-temperature method for oxidizing uranium-bearing steel alloys. Traditional laboratory-scale synthesis methods often fail to replicate the thermal and kinetic conditions experienced by real-world particulates, particularly those formed under rapid quenching or high-temperature scenarios. Combustion synthesis offers a promising alternative by enabling fast, localized heating and flexible precursor selection. A series of targeted experiments were conducted using a U 2 NiCrFe 4 alloy as the precursor. The alloy was oxidized using combustion synthesis reactions fueled by uranyl nitrate and glycine, achieving peak temperatures exceeding 1,200 °C. Postreaction analysis using scanning electron microscopy (SEM), elemental mapping, and Raman spectroscopy revealed the formation of iron-based oxides, with limited but detectable evidence of uranium oxide phases such as UO 2 . The results indicate that under the rapid reaction and cooling conditions of combustion synthesis, iron oxides form preferentially, but uranium oxide formation is kinetically limited. These findings validate combustion synthesis as a viable method for simulating the oxidation behavior of uranium steels in extreme environments and lay the groundwork for future studies aimed at enhancing uranium oxide formation through higher temperatures or modified precursor compositions.

36 MATERIALS SCIENCE↗

Heterogeneous microstructure of yttrium hydride and its relation to mechanical properties

Here, the goal of this study is to investigate the properties of yttrium hydride materials in relation to the microstructure, especially its homogeneity. High-throughput nanoindentation mapping was used to evaluate hardness distribution. Raman spectral imaging demonstrated its sensitivity to the presence of YH2 and impurities. Raman peak position maps were correlated with residual stress in the specimens. Electron backscatter diffraction mapping provided phase distributions with correlation to high-energy X-ray diffraction analysis. The experimental mapping data were combined and analyzed using unsupervised machine learning cluster procedures. The machine learning analysis revealed that yttrium hydride specimens contained a major δ-YH2 – x phase component and minor α-Y and δ-YH2 – x components with significant residual stress. The minor phase fraction decreased with increasing nominal H/Y ratio, which affected the nanoindentation and Vickers hardness. The multimodal mapping procedures described herein affect developing important microstructure–property relationships, as well as correlations in heterogeneity and mechanical properties.

36 MATERIALS SCIENCE↗

Visualizing conical intersection passages via vibronic coherence maps generated by stimulated ultrafast X-ray Raman signals

Significance The capabilities of modern X-ray sources have substantially increased the temporal and spectral resolutions for the observation of elementary molecular events. Theoretically, it has been shown that these unique features can be exploited to probe vibronic coherences that emerge when molecules pass through conical intersections. Here, we demonstrate this technique for the photorelaxation of the RNA-nucleobase uracil after UV excitation. The generated coherence maps reveal the path of the nuclear wavepacket on the excited-state surface in the vicinity of the conical intersection. This information is directly accessible from the spectroscopically recorded signal. Being transferrable to other molecules, these coherence maps will provide detailed visualizations of other nonadiabatic passages in the future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Micro-segregation phenomena and related spectroscopic signals in melt-grown β-Ga2O3 single crystals

One of the primary advantages of β-Ga2O3 over incumbent wide bandgap semiconductors is the ability to grow directly from the melt. Melt growth, using Czochralski or similar methods, results in impurities in the crystal which originate from the crucible, such as iridium and other transition metals like chromium. These impurities exhibit optoelectronic signatures useful for their identification and sensitive to the Fermi energy of a given crystal (i.e., signatures vary with the electrical conductivity of the matrix). In this work, we describe how laser Raman systems can be used to map and spatially correlate Cr3+ photoluminescence, electronic-coupled Raman scattering from Ir4+d–d internal transitions, and the Raman line attributed to hydrogenic shallow donors. Laser ablation inductively coupled plasma mass spectrometry directly measured spatially dependent relative metal concentrations and confirmed spectroscopic signals resulting from heterogeneities in impurity concentrations in β-Ga2O3 boules. Mapping of photoluminescence and Raman-related signatures is, thus, demonstrated as an effective and facile method for spatial measurement of chemical heterogeneities in both insulating and conductive melt-grown β-Ga2O3 crystals.

Dutton, Benjamin L. (ORCID:000000031272130X)↗

Spatially Mapping the CO 2 Alkaline Sorbent Diffuse Microenvironment Using Operando Raman Spectroscopy

When designing a chemical process, the local balance of transport and kinetics, collectively referred to as the diffuse microenvironment, plays a critical role in performance but is difficult to directly observe. This work demonstrates a method of two-dimensional spatial chemical mapping of the diffuse microenvironment in the context of alkali metal hydroxide direct air capture of carbon dioxide using a custom operando gas-absorption flow cell along with confocal Raman spectroscopy. Notably, we observe the concentration boundary layer near the gas–liquid interface and elucidate the interplay of carbonate and bicarbonate ions within it while inferring local hydroxide depletion through continuum modeling. These first of their kind observations provide a technique to compare the performance of direct air capture solvents based on diffuse microenvironment dynamics while also providing metrics important for air contactor design such as boundary layer thickness. Overall, this work showcases a new experimental platform to study interfacial diffuse microenvironments in and outside of the field of direct air capture of carbon dioxide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Perseverance’s Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) Investigation

The Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) is a robotic arm-mounted instrument on NASA’s Perseverance rover. SHERLOC has two primary boresights. The Spectroscopy boresight generates spatially resolved chemical maps using fluorescence and Raman spectroscopy coupled to microscopic images (10.1 μm/pixel). The second boresight is a Wide Angle Topographic Sensor for Operations and eNgineering (WATSON); a copy of the Mars Science Laboratory (MSL) Mars Hand Lens Imager (MAHLI) that obtains color images from microscopic scales (~13 μm/pixel) to infinity. SHERLOC Spectroscopy focuses a 40 μs pulsed deep UV neon-copper laser (248.6 nm), to a ~100 μm spot on a target at a working distance of ~48 mm. Fluorescence emissions from organics, and Raman scattered photons from organics and minerals, are spectrally resolved with a single diffractive grating spectrograph with a spectral range of 250 to ~370 nm. Because the fluorescence and Raman regions are naturally separated with deep UV excitation (<250 nm), the Raman region ~ 800 – 4000 cm -1 (250 to 273 nm) and the fluorescence region (274 to ~370 nm) are acquired simultaneously without time gating or additional mechanisms. SHERLOC science begins by using an Autofocus Context Imager (ACI) to obtain target focus and acquire 10.1 μm/pixel greyscale images. Chemical maps of organic and mineral signatures are acquired by the orchestration of an internal scanning mirror that moves the focused laser spot across discrete points on the target surface where spectra are captured on the spectrometer detector. ACI images and chemical maps (< 100 μm/mapping pixel) will enable the first Mars in situ view of the spatial distribution and interaction between organics, minerals, and chemicals important to the assessment of potential biogenicity (containing CHNOPS). Single robotic arm placement chemical maps can cover areas up to 7x7 mm in area and, with the < 10 min acquisition time per map, larger mosaics are possible with arm movements. This microscopic view of the organic geochemistry of a target at the Perseverance field site, when combined with the other instruments, such as Mastcam-Z, PIXL, and SuperCam, will enable unprecedented analysis of geological materials for both scientific research and determination of which samples to collect and cache for Mars sample return.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Enhanced upconversion and photoconductive nanocomposites of lanthanide-doped nanoparticles functionalized with low-vibrational-energy inorganic ligands

Upconverting nanoparticles (UCNPs) convert near-infrared (IR) light into higher-energy visible light, allowing them to be used in applications such as biological imaging, nano-thermometry, and photodetection. It is well known that the upconversion luminescent efficiency of UCNPs can be enhanced by using a host material with low phonon energies, but the use of low-vibrational-energy inorganic ligands and non-epitaxial shells has been relatively underexplored. Here, we investigate the functionalization of lanthanide-doped NaYF4 UCNPs with low-vibrational-energy Sn2S64- ligands. Raman spectroscopy and elemental mapping are employed to confirm the binding of Sn2S64- ligands to UCNPs. This binding enhances upconversion efficiencies up to a factor of 16, consistent with an increase in the luminescent lifetimes of the lanthanide ions. Annealing Sn2S64--capped UCNPs results in the formation of a nanocomposite comprised of UCNPs embedded within an interconnected matrix of SnS2, enabling each UCNP to be electrically accessible through the semiconducting SnS2 matrix. This facilitates the integration of UCNPs into electronic devices, which we demonstrate through the fabrication of a UCNP-SnS2 photodetector that detects UV and near-IR light. Our findings show the promise of using inorganic capping agents to enhance the properties of UCNPs while facilitating their integration into optoelectronic devices.

Pan, Jia-Ahn↗

Detection of high energy ionizing radiation using deeply depleted graphene–oxide–semiconductor junctions

Graphene’s linear band structure and two-dimensional density of states provide an implicit advantage for sensing charge. Here, these advantages are leveraged in a deeply depleted graphene–oxide–semiconductor (D2GOS) junction detector architecture to sense carriers created by ionizing radiation. Specifically, the room temperature response of a silicon-based D2GOS junction is analyzed during irradiation with 20 MeV Si4+ ions. Detection was demonstrated for doses ranging from 12 to 1200 ions with device functionality maintained with no substantive degradation. To understand the device response, D2GOS pixels were characterized post-irradiation via a combination of electrical characterization, Raman spectroscopy, and photocurrent mapping. This combined characterization methodology underscores the lack of discernible damage caused by irradiation to the graphene while highlighting the nature of interactions between the incident ions and the silicon absorber.

Ruiz, Isaac↗

Response of the mode Grüneisen parameters with anisotropic compression: A pressure and temperature dependent Raman study of β-Sn

The lattice dynamic response of body-centered tetragonal beta-Sn (I4 1 /amd) under high-pressure and temperature conditions is determined using experimental optical vibration modes. Here, Raman scattering is used to map the phase stability region of beta-Sn to perform mode Gruneisen analysis, and we demonstrate the necessity of an optical intensity calibration for Raman thermometry. The Gruneisen tensor is evaluated along a set of isotherms to address shortcomings of single-mode Gruneisen parameters with respect to anisotropic deformations of this tetragonal structured soft metal. The changes observed here in the Gruneisen tensor as a function of temperature are related to anharmonicity and denote potential criteria for the onset of premelting.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Generalized synthesis of high surface area mesoporous metal titanates as efficient heterogeneous catalysts

A novel metal dissolution coupled with reverse micelle formation approach is used as a generalized synthesis method for a series of high surface area metal titanates where the metals used are Bi, Mg, V, Mn, Fe, Co, Ni, Cu, Zn, Mo, W, and Ce. This study reports the highest surface areas published so far. The homogeneous distributions of the metals and titanium are observed in SEM-EDX and TEM mapping. The synthesized materials were comprehensively characterized using PXRD, Raman, nitrogen adsorption isotherms, SEM; EDX, TEM, TEM mapping, TGA, and XPS. The green catalytic oxidation of aniline to nitrosobenzene occurs within 30 min at room temperature when mesoporous W/Ti binary metal oxide is used as the catalyst. The radical mediated catalytic reaction gives excellent yields and the catalyst is reusable up to 4 reaction cycles without losing significant activity.

36 MATERIALS SCIENCE↗

Characterization of SiO 2 Thermally Grown Oxide Stress Evolution of EBCs with Al-Containing Dopants

SiC/SiC ceramic matrix composites (CMCs) are desired for use in combustion environments to achieve higher turbine operating temperatures. However, CMCs require environmental barrier coatings (EBCs) for protection from the gas environment. EBC systems are known to primarily fail through coating delamination via growth of a thermally grown oxide (TGO) at the EBC—silicon bond coating interface when exposed to steam, which accelerates the TGO growth rate. The TGO undergoes a phase transformation during thermal cycling, which results in stresses that may encourage EBC spallation. Yb-silicate EBCs with mullite and yttrium aluminum garnet (YAG) dopant additions were deposited on SiC substrates with a Si intermediate bond coating and exposed to thermal cycling in steam at 1350 °C. The impact of Al dopant additions on the TGO growth rate and the SiO 2 phase transformation was assessed. Photo-stimulated luminescence spectroscopy (PSLS) was used to characterize the Al-containing phases and to measure stress evolution in the EBC following exposure using the stress-induced peak shift of the R-lines of mullite. Raman microscopy was used to map the stresses in the Si bond coating following exposure. It was found that the TGO phase transformation upon cooling increased compressive stress in the Si bond coating within 15 µm of the TGO.

Building Materials↗

In-vivo Raman microspectroscopy reveals differential nitrate concentration in different developmental zones in Arabidopsis roots

Abstract Background Nitrate (NO 3 − ) is one of the two major forms of inorganic nitrogen absorbed by plant roots, and the tissue nitrate concentration in roots is considered important for optimizing developmental programs. Technologies to quantify the expression levels of nitrate transporters and assimilating enzymes at the cellular level have improved drastically in the past decade. However, a technological gap remains for detecting nitrate at a high spatial resolution. Using extraction-based methods, it is challenging to reliably estimate nitrate concentration from a small volume of cells (i.e., with high spatial resolution), since targeting a small or specific group of cells is physically difficult. Alternatively, nitrate detection with microelectrodes offers subcellular resolution with high cell specificity, but this method has some limitations on cell accessibility and detection speed. Finally, optical nitrate biosensors have very good ( in-vivo ) sensitivity (below 1 mM) and cellular-level spatial resolution, but require plant transformation, limiting their applicability. In this work, we apply Raman microspectroscopy for high-dynamic range in-vivo mapping of nitrate in different developmental zones of Arabidopsis thaliana roots in-situ . Results As a proof of concept, we have used Raman microspectroscopy for in-vivo mapping of nitrate content in roots of Arabidopsis seedlings grown on agar media with different nitrate concentrations. Our results revealed that the root nitrate concentration increases gradually from the meristematic zone (~ 250 µm from the root cap) to the maturation zone (~ 3 mm from the root cap) in roots grown under typical growth conditions used for Arabidopsis, a trend that has not been previously reported. This trend was observed for plants grown in agar media with different nitrate concentrations (0.5–10 mM). These results were validated through destructive measurement of nitrate concentration. Conclusions We present a methodology based on Raman microspectroscopy for in-vivo label-free mapping of nitrate within small root tissue volumes in Arabidopsis. Measurements are done in-situ without additional sample preparation. Our measurements revealed nitrate concentration changes from lower to higher concentration from tip to mature root tissue. Accumulation of nitrate in the maturation zone tissue shows a saturation behavior. The presented Raman-based approach allows for in-situ non-destructive measurements of Raman-active compounds.

Fernández González, Alma↗

Mapping Molecular Adsorption Configurations with < 5 nm Spatial Resolution through Ambient Tip-Enhanced Raman Imaging

We interrogate para-mercaptobenzoic acid (MBA) molecules chemisorbed onto plasmonic silver nanocubes through tip-enhanced Raman (TER) spectral nano-imaging. Through a detailed examination of the spectra, aided by correlation analysis and density functional theory calculations, we find that MBA chemisorbs onto the plasmonic particles with at least two distinct configurations: S- and CO2-bound. High spatial resolution TER mapping allows us to distinguish between the distinct adsorption geometries with a pixel-limited (< 5 nm) spatial resolution under ambient laboratory conditions.

Gabel, Matthew L.↗

Ferroelastic Domain-Induced Electronic Modulation in Halide Perovskites

Lead halide perovskites have emerged as promising materials for optoelectronic applications due to their exceptional properties. In the all-inorganic CsPbBr 3 perovskites, ferroelastic domains formed during phase transitions enhance bulk transport and emissive efficiency. However, the microscopic mechanisms governing carrier dynamics remain poorly understood. In this study, we employ cathodoluminescence (CL) and micro-Raman spectroscopy to image and investigate the electronic properties of the ferroelastic domain walls in CsPbBr 3 single crystals. CL measurements reveal a reduced emissive yield and a slight redshift in emission at the domain walls. Further, micro-Raman studies provide spatially resolved mapping of vibrational modes, exhibiting second-order phonon modes localized at the domain boundaries. In conclusion, our findings suggest that electron–phonon coupling at the twin domain walls plays a critical role in facilitating efficient charge separation, thereby improving the optoelectronic performance of the CsPbBr 3 perovskites.

Carrier dynamics↗

AFM-IR and s-SNOM-IR measurements of chemically addressable monolayers on Au nanoparticles

The performance of catalysts depends on their nanoscale properties, and local variations in structure and composition can have a dramatic impact on the catalytic reactivity. Therefore, probing the localized reactivity of catalytic surfaces using high spatial resolution vibrational spectroscopy, such as infrared (IR) nanospectroscopy and tip-enhanced Raman spectroscopy, is essential for mapping their reactivity pattern. Two fundamentally different scanning probe IR nanospectroscopy techniques, namely, scattering-type scanning near-field optical microscopy (sSNOM) and atomic force microscopy-infrared spectroscopy (AFM-IR), provide the capabilities for mapping the reactivity pattern of catalytic surfaces with a spatial resolution of ~20 nm. Herein, we compare these two techniques with regard to their applicability for probing the vibrational signature of reactive molecules on catalytic nanoparticles. For this purpose, we use chemically addressable self-assembled molecules on Au nanoparticles as model systems. We identified significant spectral differences depending on the measurement technique, which originate from the fundamentally different working principles of the applied methods. While AFM-IR spectra provided information from all the molecules that were positioned underneath the tip, the s-SNOM spectra were more orientation-sensitive. Due to its field-enhancement factor, the s-SNOM spectra showed higher vibrational signals for dipoles that were perpendicularly oriented to the surface. The s-SNOM sensitivity to the molecular orientation influenced the amplitude, position, and signal-to-noise ratio of the collected spectra. Ensemble-based IR measurements verified that differences in the localized IR spectra stem from the enhanced sensitivity of s-SNOM measurements to the adsorption geometry of the probed molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spatially Resolved Raman Spectroscopy of Thin Carbon Interphase in SiC Ceramic Matrix Composites

A dedicated analysis method is presented to extract the Raman spectrum of an interphase layer thinner than the laser spot size. We focused on spatial correlations between the contrast of optical micrographs and Raman hyperspectral data to predict the constituents of the mixed spectra measured near the interphase. By employing a mapping step size of 0.1 μm, the Raman spectrum of approximately 0.3-μm-thick carbon interphase in a SiC fiber-reinforced SiC matrix composite was extracted from data acquired with a theoretical spot size of about 0.7 μm. Notably, conventional chemometrics procedures were unable to isolate the interphase signal, instead producing a spectrum representing a mixture of interphase and matrix. This study used another composite with approximately 0.9-μm-thick interphase to validate the analysis method, enabling direct measurement of the interphase spectrum. The proposed Raman analysis method has advantages in specimen volume and turnaround time compared to traditional characterization methods, such as transmission electron microscopy. In conclusion, this study also evaluates the applicability of the analysis method to different composite materials and identifies key requirements of the measurements, including the ratio of interphase thickness to spot size and the homogeneity of the surrounding matrix.

ceramic matrix composite↗

Bridging Structure, Magnetism, and Disorder in Iron-Intercalated Niobium Diselenide, Fe x NbSe 2 , below x = 0.25

Transition-metal dichalcogenides (TMDs) intercalated with magnetic ions serve as a promising materials platform for developing next-generation, spin-based electronic technologies. In these materials, one can access a rich magnetic phase space depending on the choice of intercalant, host lattice, and relative stoichiometry. The distribution of these intercalant ions across given crystals, however, is less well defined–particularly away from ideal packing stoichiometries–and a convenient probe to assess potential longer-range ordering of intercalants is lacking. Here, we demonstrate that confocal Raman spectroscopy is a powerful tool for mapping the onset of intercalant superlattice formation in Fe-intercalated NbSe 2 (Fe x NbSe 2 ) for 0.14 ≤ x < 0.25. We use single-crystal X-ray diffraction to confirm the presence of longer-range intercalant superstructure and employ polarization-, temperature-, and magnetic field-dependent Raman measurements to examine both the symmetry of emergent phonon modes in the intercalated material and potential magnetoelastic coupling. Magnetometry measurements further indicate a correlation between the onset of magnetic ordering and the relative degree of intercalant superlattice formation. These results show Raman spectroscopy to be an expedient, local probe for mapping intercalant ordering in this class of magnetic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗