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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

BCARS Simulated Phantom Dataset for Evaluation of Processing Pipelines

Broadband coherent anti-Stokes Raman scattering (BCARS) microscopy is a powerful label-free biological imaging technique, but the raw signal requires careful processing. The vibrationally resonant (Raman) fingerprint signal is usually small compared with instrumental noise sources and the nonresonant background (NRB) inherent in the BCARS signal. Fortunately, the NRB exhibits a systematic phase relationship with the coherent Raman response, acting as a heterodyne amplifier for the weak fingerprint signal. Due to this heterodyne effect, the Raman response can be recovered quantitatively and invariantly across different instruments, provided the NRB shape is known. Even with heterodyne amplification, the amplitudes of fingerprint signal components are often comparable to system noise. Singular value decomposition (SVD), which utilizes spatial information, is often employed for additional noise filtering. Consequently, finding optimal processing parameters to properly distinguish the NRB and Raman responses and suppress noise in the complex BCARS signal requires a reference system that realistically represents the spectral and spatial properties of BCARS signals obtained from biological samples. We present a digital tissue phantom that meets these criteria as a tool for testing candidate signal processing pipelines. The digital phantom is generated with simulated hyperspectral Raman images having system-specific noise and background characteristics. Here, we analyze phantom datasets with differing background and signal-to-noise conditions to evaluate their impact on the performance of multiple signal processing pipelines. Specifically, we investigate the application of a Butterworth filter-based routine to directly estimate the NRB from the BCARS signal. Additionally, we evaluate a Lorentzian wavelet transform as an alternative to the Hilbert transform for extracting the Raman spectrum from the BCARS signal. While we demonstrate this phantom for BCARS, it can be used for any spectroscopic Raman imaging approach.

Dixon, Jessica Z. [Georgia Institute of Technology↗
DOE OSTI2020

Observation of intravalley phonon scattering of 2s excitons in MoSe 2 and WSe 2 monolayers

Abstract We present a high-resolution resonance Raman study of hBN encapsulated MoSe 2 and WSe 2 monolayers at 4 K using excitation energies from 1.6 eV to 2.25 eV. We report resonances with the WSe 2 A2s and MoSe 2 A2s and B2s excited Rydberg states despite their low oscillator strength. When resonant with the 2s states we identify new Raman peaks which are associated with intravalley scattering between different Rydberg states via optical phonons. By calibrating the Raman scattering efficiency and separately constraining the electric dipole matrix elements, we reveal that the scattering rates for k = 0 optical phonons are comparable for both 1s and 2s states despite differences in the envelope functions. We also observe multiple new dispersive Raman peaks including a peak at the WSe 2 A2s resonance that demonstrates non-linear dispersion and peak-splitting behavior that suggests the dispersion relations for dark excitonic states at energies near the 2s state are extremely complex.

Materials Science↗
DOE OSTI2024

The effects of thickness, polarization, and strain on vibrational modes of 2D Fe 3 GeTe 2

In this study, we investigated the effects of thickness, light polarization, and strain on the Raman spectra of two-dimensional (2D) Fe 3 GeTe 2 (FGT) crystals synthesized via chemical vapor transport. The crystals are thoroughly characterized using a combination of microscopic, diffraction, and spectroscopic techniques. Particularly, a systematic angle-resolved polarized Raman spectroscopy study reveals a clear polarization dependence of the Raman intensity in both parallel and crossed polarization directions, with the $A$$^{1}_{g}$ mode completely disappearing in the crossed polarization direction. The angle-dependent intensity of both the $A$$^{1}_{g}$ and $E$$^{2}_{2g}$ modes in parallel polarization and the intensity of the $E$$^{2}_{2g}$ mode in the crossed polarization remain constant at all angles. These findings align with predictions from Raman tensor analysis, providing compelling evidence for the unambiguous assignment of the $A$$^{1}_{g}$ and $E$$^{2}_{2g}$ modes to specific peaks observed in the Raman spectrum of FGT, resolving existing confusion in the literature regarding their assignment. Furthermore, we examine the effect of strain on the Raman spectrum of 2D FGT in-situ using a bending device. Our study, conducted on a monolayer to few-layer 2D FGT deposited onto polyethylene terephthalate and subjected to outward (inward), i.e., tensile (compressive) bending, demonstrates appreciable downshifting (upshifting) of the Raman peak position of both $A$$^{1}_{g}$ and $E$$^{2}_{2g}$ modes. Furthermore, these findings are particularly significant given that strain engineering represents an effective approach to modulate the magnetic properties of FGT and other 2D magnetic materials.

2D materials↗
DOE OSTI2020

Trace Chemical Detection Using Intercalated MXenes as a Signal Enhancing Substrate in Optical Probes

MXenes are 2D materials composed of layered transition metal nitrides or carbides. These materials are synthesized by HF exfoliation from MAX phases (Ti{sub 3}AlC{sub 2}). The 2D nanomaterial was synthesized by the removal of the 'A' element, resulting in a Mxene product (Ti{sub 3}C{sub 2}). MXenes have the general formula M{sub n+1}X{sub n}T{sub x}, where M is an early transition metal, X is Carbon and/or Nitrogen, and T accounts for surface terminated functional groups such as Fluoride, hydroxyl, and oxygen. These materials have very unique properties, similar to graphene, that allows them to be applied in a variety of trace detection techniques including surface-enhanced Raman spectroscopy (SERS). MXenes have also been demonstrated to selectively uptake uranyl ion, UO{sub 2}{sup 2+}. If this property can be combined with SERS or fluorescence detection, it may be possible to use MXenes as the basis for an alternative method to kinetic phosphorescence analysis (KPA) for trace uranyl measurements. Objectives: To confirm that MXene Nano materials are suitable substrates for SERS and sensor development by enhancing Raman signaling. To determine if certain MXene preparation methods yield materials that are more suitable for trace sensing methods. To determine uranyl uptake properties of these MXene materials and test them for analytical signals. Sample Preparation: Preparation of Ti{sub 3}C{sub 2}MXene (at FSU). MXenes were prepared by etching Al from Ti{sub 3}AlC{sub 2} (MAX phase)material. Two etching techniques yield different MXene products: LiF/HCl: Milder reaction, larger MXene flakes. HF: Harsher reaction, smaller flakes, larger layer separation. Products washed to remove etchant, vacuum filtered, and dried. Dried MXene flakes are air-stable. Film preparation for sensor testing (at SRNL): Suspend powder in diH{sub 2}O, purge with Ar, sonicate for 30 min. Centrifuge and collect supernate with suspended particles. Observed LiF-etched Mxene yielded a higher density of particles and darker collected solution. Drop-cast (4 ml) supernate onto slides and dried with Ar. For Rhodamine B (RhB) testing, drop-cast 4 ml drops onto Mxene spots and dried with Ar. Scanning Electron Microscopy conditions: 10 kV Beam energy, high vacuum; Working distance of 8 mm; beam penetration depth appx. 4 microns, beam spot size appx. 2 nanometers. Results: Detection of aluminum correlates with bright spots on image. Presence of aluminum shows that LiF/HCl etching was less thorough than HF etching. Trace Cl detection in LiF images suggests incomplete rinsing. HF has smaller feature size, more layer structure, and increased homogeneity, consistent with expectations. Macroscopic Raman spectroscopy measurements: 532 nm excitation, ∼50 mW with a ∼100 micron spot size (InPhotonics RPB probe). Kaiser Optical Holospec f/1.8 spectrometer with cooled (-60 deg.C) Andor iDus OE420 CCD. LiF 1x supernate showed good signal for trace measurements of Rhodamine B. HF and 1/4x LiF supernates showed little Mxene or Rhodamine B signal. Low deposition densities led to excess background signal from glass slides. For LiF film, response is linear with Rhodamine B concentration over range tested. Will retest with Raman microscope (∼1 micron spot size) to characterize SERS of more dilute LiF and HF etched Mxenes. Conclusions: The LiF etched material was more suitable for macroscopic SERS measurements because it was more concentrated, resulting in a thicker film than the HF etched Mxene and diluted LiF sample. However, the other materials may give greater SERS enhancements, which we hope to determine from measurements with the Raman microscope. From characterization with SEM we concluded that the HF etched Mxene is more uniform/homogenous and has smaller particle size than the LiF etched Mxene. There is still aluminum present in both samples indicating that etching wasn't complete, but the removal of the aluminum was more efficient in the HF method. Path Forward: Observe SERS with Raman microscopy, to obtain better signals for the more diluted samples and be able to compare enhancement effects for the different MXenes. Characterize uranyl sorption into MXene films and test Raman and fluorescence signals. Revisit the etching conditions to improve removal of aluminum. FSU and SRNL will continue to collaborate to create and characterize different Mxene materials and test their usefulness for sensor applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

Non-intrusive measurements in a rocket engine combustor

In recent years analytical tools to characterize combustor flow have been developed in order to support design. To facilitate anchoring of combustion related physical models and the CFD codes in which they are incorporated, considerable development and application of non-intrusive combustion diagnostic capabilities has occurred. Raman spectroscopy can be used to simultaneously detect all polyatomic molecules present in significant concentrations and to determine gas temperature. This is because all molecules possess a distinct temperature dependent Raman spectrum. A multi-point diagnostic system for non-intrusive temperature and species profiling in rocket engines has been developed at Rocketdyne. In the present effort, the system has been undergoing validation for application to rocket engine component testing. A 4 inch diameter windowed combustor with a coaxial gas-gas injector was chosen for this series of validation experiments. Initially an excimer-pumped tunable dye laser and later a solid state Nd-Yag laser served as excitation sources. The Raman signal was dispersed by a monochromator and detected by a gated, intensified Charged Coupled Device (CCD) array. Experiments were carried out prior to each series of hot fire tests to ensure that the Raman signal detected was due to a spontaneous rather than a stimulated Raman emission process. Over sixty hot fire tests were conducted during the first series of tests with the excimer/dye laser. All hot fire testing was at a mixture ratio of 0.5 and chamber pressures of approximately 100 and approximately 300 psia. The Raman spectra of hydrogen, water vapor and oxygen recorded during single element hot fire tests were reduced and analyzed. A significant achievement was the attainment of single shot Raman spectra in cold flow tests. Unfortunately, the single shot signal-to-noise ratio deteriorated to an unacceptable level during the hot fire testing. Attempts to obtain temperature data from the hydrogen Q1-branch profiles obtained in hot fire tests suggest that potentially complicating factors may render the approach of averaging data on the photodiode array invalid. A second series of hot fire tests was conducted with a 4 element coaxial injector using the Nd-Yag laser. A very compact and portable diagnostics set up was assembled for ease of alignment, relocation and flexibility. Measurements were made at several regions in the chamber in order to map concentration profiles. High spatial resolution and improved signal to noise characteristics were demonstrated.

Farhangi, S.↗
NASA NTRS1996

Trace Element Zoning and Incipient Metamictization in a Lunar Zircon: Application of Three Microprobe Techniques

We have determined major (Si, Zr, Hf), minor (Al, Y, Fe, P), and trace element (Ca, Sc, Ti, Ba, REE, Th, U) concentrations and Raman spectra of a zoned, 200 microns zircon grain in lunar sample 14161,7069, a quartz monzodiorite breccia collected at the Apollo 14 site. Analyses were obtained on a thin section in situ with an ion microprobe, an electron microprobe, and a laser Raman microprobe. The zircon grain is optically zoned in birefringence, a reflection of variable (incomplete) metamictization resulting from zo- nation in U and Th concentrations. Variations in the concentrations of U and Th correlate strongly with those of other high-field-strength trace elements and with changes in Raman spectral parameters. Concentrations of U and Th range from 21 to 55 ppm and 6 to 31 ppm, respectively, and correlate with lower Raman peak intensities, wider Raman peaks, and shifted Si-O peak positions. Concentrations of heavy rare earth elements range over a factor of three to four and correlate with intensities of fluorescence peaks. Correlated variations in trace element concentrations reflect the original magmatic differentiation of the parental melt approx. 4 b.y. ago. Degradation of the zircon structure, as reflected by the observed Raman spectral parameters, has occurred in this sample over a range of alpha-decay event dose from approx. 5.2 x 10(exp 14) to 1.4 x 10(exp 15) decay events per milligram of zircon, as calculated from the U and Th concentrations. This dose is well below the approx. 10(exp 16) events per milligram cumulative dose that causes complete metamictization and indicates that laser Raman microprobe spectroscopy is an analytical technique that is very sensitive to the radiation-induced damage in zircon.

Wopenka, Brigitte↗
DOE OSTI2022

Unexpected features in the optical vibrational spectra of δ-UO 3

Uranium trioxide displays a complex chemical phase space, with at least six structurally distinct polymorphs accessible via different synthetic routes. Remarkably, despite its technological importance, full structural and electronic characterization of these polymorphs remains an open area of study. δ-UO 3 in particular has attracted significant theoretical attention due to its high point group and space group symmetries, having U (VI) in octahedral coordination with polyhedra interconnected through corner-sharing to build a 3-D cubic lattice with space group symmetry Pm-3m and Z = 1. Critical experimental information, such as its optical vibrational spectra, are not known. Here, we study the Raman and infrared (IR) spectra of δ-UO 3 together with the support of density functional theory (DFT) calculations for spectral interpretation. A symmetry analysis of the DFT-predicted phonon eigenmodes indicates that δ-UO 3 should have two IR active modes and no Raman active modes. Experimental results, however, indicate significant Raman scattering from δ-UO 3 . We therefore propose four potential explanations for this apparent contradiction: a possible tetragonal distortion to the cubic cell, the existence of a surface impurity layer, vacancy scattering, and structural activation of Raman signal. We use powder X-ray diffraction and confocal Raman spectroscopy with depth profiling to investigate these possibilities and suggest future experiments to explore this phenomenon in more detail. Understanding the lattice dynamics of δ-UO 3 is important for identification of technogenic U phases via Raman and infrared spectroscopy and our results indicate that the simple understanding of δ-UO 3 as a high-symmetry cubic structure should be reconsidered.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2026

Crystal Orientation Independent Strong TERS Response in Anisotropic ReS2 on Gold

Rhenium disulfide (ReS2) crystallizes in a distorted 1T' lattice with triclinic symmetry arising from Re–Re dimerization, which produces in-plane anisotropic properties and a dense set of Raman-active modes with mixed atomic displacements. Unlike far-field Raman spectroscopy, which shows strong polarization and orientation dependence, tip-enhanced Raman spectroscopy (TERS) probes out-of-plane Raman tensor components. Here we use 785 nm (1.58 eV) gap-mode TERS to investigate monolayer to four-layer thick ReS2 crystals.. TERS maps and averaged spectra reveal that all modes remain invariant under 90° rotation of the crystal, and the only thickness-dependent feature is the emergence of the multilayer breathing mode. These results demonstrate that TERS yields a crystal-orientation-independent Raman response in ReS2 and provides direct access to Raman tensor components that are not easily accessible in conventional far-field measurements.

Valencia Acuna, Pavel A.↗
DOE OSTI2026

Optical Vibrational Spectroscopic Investigation of Natural and Synthetic Analogs of Uranyl Oxyhydroxyhydrate Minerals

Uranyl oxy-hydroxy-hydrate minerals are common alteration products of uraninite (UO2+x) which is chemically and structurally analogous to uranium dioxide nuclear fuel. Therefore, structural and spectroscopic investigations of these alteration minerals and their analogous anthropogenic counterparts can provide insight into the environmental behavior of nuclear fuel cycle materials. Previously, we compiled available vibrational spectroscopic data for uranyl minerals in the Compendium of Uranium Raman and Infrared Experimental Spectra (CURIES) and found that only 37% of known uranyl oxy-hydroxy-hydrate minerals had spectra readily available in the literature and existing databases for inclusion therein. Furthermore, no available infrared spectra for this mineral group were included in CURIES. To expand our understanding of the spectroscopic features of uranyl oxy-hydroxy-hydrates and the structural origins thereof, we collected, and now include in CURIES, Raman and infrared spectra for an additional 12 uranyl hydroxide phases. To better understand the impact of structural and compositional variations of these phases on their spectroscopic features, we compare Raman spectra of different anion sheet topological groups and of analogous phases hosting different counter cations. We identify spectroscopic variations related to differences in equatorial bonding and structural changes as a result of cation substitution. We also prepare a uranyl hydroxide phase via hydrolysis of uranyl fluoride (UO2F2) as an analog of hydrolysis reactions that occur in nuclear fuel cycle materials; and we find that the alteration product of UO2F2, despite chemical and structural similarities to uranyl oxy-hydroxy-hydrate minerals, is readily distinguishable from related mineral phases using Raman spectroscopy. In this work, we provide new insights into the structural origins of spectroscopic features in uranyl oxy-hydroxy-hydrate minerals, improve the average Raman spectrum for this group of minerals, and thereby improve capabilities for identifying these mineral species and related anthropogenic phases using Raman spectroscopy.

Barth, Brodie [ORNL] (ORCID:0000000256142601)↗
DOE OSTI2025

An Investigation of Thermal Properties of 2D Materials [Dissertation]

Studying the thermal conductivity of 2D materials is important due to the applications of 2D materials in fields such as thermal management, thermoelectricity, renewable energy, and sensors. As such, measurements of the thermal conductivity of these 2D materials become important to measure. Thermal conductivity is often difficult to measure for 2D materials due to their atomically thin nature and many experimental methods for doing so requiring contact with the sample, which can alter the thermal properties. A non-contact method for calculating the thermal conductivity of 2D materials supported on substrates in order to model the thermal conductivity of 2D materials for devices, is proposed and experimentally performed in this dissertation. The optothermal Raman technique is a useful non-contact diagnostic technique useful in determining the thermal conductivity of 2D materials. The optothermal Raman typically does not account for heat losses due to convection or radiation or substrate resistance, which are shown to be important factors to consider when developing an optothermal Raman model. Additionally, the calculation of the interfacial thermal conductance between the bottom surface of the sample and the top surface of the substrate, plays an important role in determining the final value of the thermal conductivity of a supported sample, and will yield differing results based on whether or not the conductance is calculated using an approach such as the Diffuse Mismatch Model (DMM) or calculated directly by varying the laser heating profile (usually done by changing the laser objective). This is shown to be the case for both graphene on Ni, graphene on Cu, and SnSe 2 on Cu. In addition to experimentally calculating the thermal conductivity of a 2D material with the optothermal Raman technique, the thermal conductivity of 2D materials can also be calculated using computational methods. The three-phonon method is a method which can be used to simulate phonon scattering processes and determine the thermal conductivity of semiconductors, wherein phonon scattering is the dominant mechanism which determines the thermal conductivity. The three-phonon method uses relaxation times for phonon scattering with other phonons, electrons, and other material system elements, such as isotopes or material defects, in order to create a single-mode relaxation time approximation (SMRTA), which is used to calculate the final value of the thermal conductivity. An important consideration when determining the thermal conductivity of a 2D material using this method is the device geometry, which is reflected in this work as the phonon-boundary scattering relaxation time. This inclusion is important along with the inclusion of phonon-electron scattering in accurately determining the thermal conductivity of a 2D material. In both the optothermal Raman experiments and the three-phonon method computations, strain is shown to have a demonstrable effect on the thermal conductivity of 2D materials. When a 1.1% strain was applied to the mechanical properties of SnSe, the three-phonon processes yielded a lower thermal conductivity than the no-strain case. For the optothermal Raman experiments, the strain induced in the Cu substrate and transferred to a single-layer graphene (SLG) sample yields a trend where the thermal conductivity of the SLG decreases with respect to strain applied. In the case where the interfacial thermal conductance was calculated directly, the conductance increased with respect to strain applied. This presents strain as a reliable and viable method for tuning the thermal properties of 2D materials for device applications.

36 MATERIALS SCIENCE↗
NASA NTRS1999

Coherent Pump-Probe Interactions and Terahertz Intersubband Gain in Semiconductor Quantum Wells

In recent years there has been considerable interest in intersubband-transition-based infrared semiconductor quantum well (QW) lasers because of their potential applications. In the mid-infrared range, both electrically-injected quantum cascade lasers [1] and optically-pumped multiple QW lasers [2] have been experimentally realized. In these studies, optical gain is due to population inversion between the lasing subbands. It was also proposed that stimulated Raman scattering in QW systems can produce net infrared optical gain [3j. In such a nonlinear optical scheme, the appearance of optical gain that may lead to intersubband Raman lasers does not rely on the population inversion. Since, in tile resonant Raman process (Raman gain is the largest in this case), the pump field induces population redistribution among subbands in the QW s ystem, it seems that a realistic estimate of the optical gain has to include this effect. Perturbative calculations used in the previous work [3] may overestimate the Raman gain. In this paper we present a nonperturbative calculation of terahertz gain of optically-pumped semiconductor step quantum wells. Limiting optical transitions within the conduction band of QW, we solve the pump-field-induced nonequilibrium distribution function for each subband of the QW system from a set of coupled rate equations. Both intrasubband and intersubband relaxation processes in the quantum well system are included. Taking into account the coherent interactions between pump and THz (signal) waves, we we derive the susceptibility of the QW system for the THz field. For a GaAs/AlGaAs step QW, we calculate the Thz gain spectrum for different pump frequencies and intensities. Under moderately strong pumping (approximately 0.3 MW/sq cm), a significant THz gain (approximately 300/m) is predicted. It is also shown that the coherent wave interactions (resonant stimulated Raman processes) contribute significantly to the THz gain.

Liu, Ansheng↗
NASA NTRS2002

High-Pressure Gaseous Burner (HPGB) Facility Completed for Quantitative Laser Diagnostics Calibration

A gas-fueled high-pressure combustion facility with optical access, which was developed over the last 2 years, has just been completed. The High Pressure Gaseous Burner (HPGB) rig at the NASA Glenn Research Center can operate at sustained pressures up to 60 atm with a variety of gaseous fuels and liquid jet fuel. The facility is unique as it is the only continuous-flow, hydrogen-capable, 60-atm rig in the world with optical access. It will provide researchers with new insights into flame conditions that simulate the environment inside the ultra-high-pressure-ratio combustion chambers of tomorrow's advanced aircraft engines. The facility provides optical access to the flame zone, enabling the calibration of nonintrusive optical diagnostics to measure chemical species and temperature. The data from the HPGB rig enables the validation of numerical codes that simulate gas turbine combustors, such as the National Combustor Code (NCC). The validation of such numerical codes is often best achieved with nonintrusive optical diagnostic techniques that meet these goals: information-rich (multispecies) and quantitative while providing good spatial and time resolution. Achieving these goals is a challenge for most nonintrusive optical diagnostic techniques. Raman scattering is a technique that meets these challenges. Raman scattering occurs when intense laser light interacts with molecules to radiate light at a shifted wavelength (known as the Raman shift). This shift in wavelength is unique to each chemical species and provides a "fingerprint" of the different species present. The facility will first be used to gather a comprehensive data base of laser Raman spectra at high pressures. These calibration data will then be used to quantify future laser Raman measurements of chemical species concentration and temperature in this facility and other facilities that use Raman scattering.

Nguyen, Quang-Viet↗
NASA NTRS2008

Microfluidics, Chromatography, and Atomic-Force Microscopy

A Raman-and-atomic-force microscope (RAFM) has been shown to be capable of performing several liquid-transfer and sensory functions essential for the operation of a microfluidic laboratory on a chip that would be used to perform rapid, sensitive chromatographic and spectro-chemical analyses of unprecedentedly small quantities of liquids. The most novel aspect of this development lies in the exploitation of capillary and shear effects at the atomic-force-microscope (AFM) tip to produce shear-driven flow of liquids along open microchannels of a microfluidic device. The RAFM can also be used to perform such functions as imaging liquids in microchannels; removing liquid samples from channels for very sensitive, tip-localized spectrochemical analyses; measuring a quantity of liquid adhering to the tip; and dip-pen deposition from a chromatographic device. A commercial Raman-spectroscopy system and a commercial AFM were integrated to make the RAFM so as to be able to perform simultaneous topographical AFM imaging and surface-enhanced Raman spectroscopy (SERS) at the AFM tip. The Raman-spectroscopy system includes a Raman microprobe attached to an optical microscope, the translation stage of which is modified to accommodate the AFM head. The Raman laser excitation beam, which is aimed at the AFM tip, has a wavelength of 785 nm and a diameter of about 5 m, and its power is adjustable up to 10 mW. The AFM is coated with gold to enable tip-localized SERS.

Anderson, Mark↗
DOE OSTI2025

Two-dimensional burn velocity and analysis of burn products of nitromethane at high pressure

We have studied the laser-initiated deflagration of nitromethane (CH 3 NO 2 ) under high static pressure in the diamond anvil cell. Time-resolved images of the deflagrations have been obtained using intensified CCDs (ICCD). In contrast with previous work, we rely on spontaneous emission from the reaction, rather than changes in the speckle pattern produced by artificial illumination of the sample. Furthermore, as opposed to the 1D records obtained previously with streak cameras, ICCDs permit imaging of the burn in two dimensions providing the ability to directly observe anisotropic deflagration behavior. Here, we report several examples of this behavior and discuss its possible origins. We have also investigated the products of the reaction using Raman spectroscopy. At pressures below 25 GPa, the burn product is observed to be opaque and has a Raman spectrum consistent with a carbonaceous soot. At pressures above 25 GPa, the burn product is observed to be transparent (consistent with earlier reports) and its Raman spectrum reveals the presence of molecular N 2 and a nitrogen-carbonate species. The latter species can be recovered to ambient pressure and has a Raman spectrum consistent with ammonium carbonate or ammonium bicarbonate. To aid interpretation of the Raman spectra, measurements have also been made on the isotopologues CH 3 15 NO 2 and 13 CH 3 NO 2 . This work establishes the importance of advanced time-resolved imaging to reveal the details of deflagration under high pressure and further advances our understanding of the corresponding chemistry.

Deflagration↗
DOE OSTI2026

Understanding the structural and morphological effects of synthesis route on NpO 2

The availability of actinide standard materials for use in nuclear safeguard applications is critical, as is thorough characterization thereof. Although accurate trace element compositions and isotopic considerations are paramount for deployment of reference standards, structural characterization is also essential towards accurately describing the chemical form and potential matrix effects in candidate materials. Here, to this end, samples of NpO 2 were synthesized via a direct denitration (DD) method and probed with powder X-ray diffraction (PXRD), Raman spectroscopy, and scanning electron microscopy (SEM) for structural and morphological characterization and comparison with NpO 2 materials produced via modified direct denitration (MDD). PXRD confirmed the bulk identity of NpO 2 , and no additional phases were identified using this method. Analysis of Raman data collected using a 532 nm excitation wavelength indicates that samples are mostly phase pure; however, some variability in spectral features is observed. Analysis of additional spectroscopic data collected with a 785 nm excitation wavelength revealed variability in the relative intensity of spectral features. Raman spectroscopy indicates that the sample is primarily NpO 2 ; however, additional signals indicate possible structural disorder, oxidized species, or potential contributions from other Np phases. To further investigate the possibility of additional phase contributions within the sample of NpO 2 , Raman spectroscopic mapping was employed to examine the homogeneity of the sample produced via DD. From this analysis, we determined that despite variability in the intensity of Raman-active vibrational modes, consistent spectra are obtained throughout the area of the sample investigated. SEM images show aggregates with variable sizes and shapes, with rounded, primary particles possessing an average diameter of approximately 100 nm. Comparison of the results of these multimodal analyses to the literature indicates that the crystal chemical, spectroscopic, and microstructural properties of NpO 2 vary based on synthesis method, even if X-ray diffraction data indicate that the bulk phase is NpO 2 .

Direct denitration↗
DOE OSTI2021

Vibrational Properties of a Naturally Occurring Semiconducting van der Waals Heterostructure

We present vibrational properties of Franckeite, which is a naturally occurring van der Waals heterostructure consisting of two different semiconducting layers. Franckeite is a complex layered crystal composed of alternating SnS 2 -like pseudohexagonal and PbS-like pseudotetragonal layers stacked on top of each other, providing a unique platform to study vibrational properties and thermal transport across layers with mass density and phonon mismatches. Using micro-Raman spectroscopy and first-principles Raman simulations, we found that the PbS-like pseudotetragonal structure is mostly composed of Pb 3 SbS 4 . We also discovered several low-frequency Raman modes that originate from the intralayer vibrations of the pseudotetragonal layer. Using density functional theory, we determined all vibrational patterns of Franckeite, whose signatures are observed in the Raman spectrum. By studying temperature-dependent Raman spectroscopy (300–500 K), we have found different temperature coefficients for both pseudotetragonal and pseudohexagonal layers. Here, we believe that our study will help understand the vibration modes of its complex heterostructure and the thermal properties at the nanoscale.

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

Interpretable machine learning models classify minerals via spectroscopy

Developing methods to identify mineral species confidently and rapidly from Raman spectral analysis is critical to numerous fields. Traditionally, analysis relies on pattern matching the Raman spectrum of an unknown dataset with a supporting library of well-characterized spectral data, which may prove difficult for environmental samples that are poorly crystalline or phase mixtures. Here, we developed interpretable machine learning models that can classify uranium minerals by secondary oxyanion chemistry and other physicochemical properties based solely on Raman spectra. This new ML method produces a mineral profile of physical and chemical properties for an unknown sample and can rapidly classify or identify unknown minerals from Raman data, without the need for an exact pattern match in a spectral library. Training models are validated by 1. Strong correlation of high confidence model regions with published spectroscopic assignments and 2. Correct classification of a mineral not present in training data. Training data are from the Compendium of Uranium Raman and Infrared Experimental Spectra and available crystallographic information files within the open-source Smart Spectral Matching scientific framework. Physically meaningful classifier models can rapidly identify key structural and chemical information about unknown uranium minerals and the overall methodology is broadly applicable for mineral phases.

Machine learning↗
DOE OSTI2022

The phononic and charge density wave behavior of entire rare-earth tritelluride series with chemical pressure and temperature

Here, we present comprehensive phononic and charge density wave properties (CDW) of rare-earth van der Waals tritellurides through temperature dependent angle-resolved Raman spectroscopy measurements. All the possible rare-earth tritellurides (RTe3) ranging from R = La–Nd, Sm, Gd–Tm were synthesized through a chemical vapor transport technique to achieve high quality crystals with excellent CDW characteristics. Raman spectroscopy studies successfully identify the emergence of the CDW state and transition temperature (TCDW), which offers a non-destructive method to identify their CDW response with micron spatial resolution. Temperature dependent Raman measurements further correlate how the atomic mass of metal cations and the resulting chemical pressure influence its CDW properties and offer detailed insight into the strength of CDW amplitude mode-phonon coupling during the CDW transition. Angle-resolved Raman measurements offer the first insights into the CDW-phonon symmetry interplay by monitoring the change in the symmetry of phonon mode across the CDW transition. Overall results introduce the library of RTe3 CDW materials and establish their characteristics through the non-destructive angle-resolved Raman spectroscopy technique.

36 MATERIALS SCIENCE↗