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At least 1,369 records · Page 76
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

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↗
DOE OSTI2019

Nanoscale Chemical Reaction Imaging at the Solid-Liquid Interface via TERS

Plasmon-enhanced chemical transformations at the solid-liquid interface can be imaged with high sensitivity, chemical selectivity, and nanoscale precision through tip-enhanced Raman scattering (TERS). We demonstrate the latter for the first time through measurements aimed at (i) locating plasmonic hotspots at the solid-liquid interface at which chemical transformations take place, (ii) monitoring the evolution from reactants to products through their distinct Raman spectra, and (iii) 2D correlation analysis of Raman time trajectories to unambiguously extract the spectral components that mark chemical transformation and to understand the correlations between the product and parent signatures. For our proof-of-principle study, we select a model plasmon-enhanced chemical process, namely, the dimerization of p-nitrothiophenol to dimercaptoazobenzene, but now, at the solid-liquid interface. Our plasmonic construct otherwise consists of chemically functionalized gold microplates in aqueous solution, which we image using a gold-coated TERS probe irradiated at 633-nm. Overall, we demonstrate chemical reaction imaging in aqueous solution via TERS for the first time, herein, at a pixel-limited lateral spatial resolution of 10 nm.

Bhattarai, Ashish↗
DOE OSTI2020

Oxide-Free Three-Dimensional Germanium/Silicon Core–Shell Metalattice Made by High-Pressure Confined Chemical Vapor Deposition

Metalattices are crystalline arrays of uniform particles in which the period of the crystal is close to some characteristic physical length scale of the material. In this work, we explore the synthesis and properties of a germanium metalattice in which the similar to 70 nm periodicity of a silica colloidal crystal template is close to the similar to 24 nm Bohr exciton radius of the nanocrystalline Ge replica. The problem of Ge surface oxidation can be significant when exploring quantum confinement effects or designing electronically coupled nanostructures because of the high surface area to volume ratio at the nanoscale. To eliminate surface oxidation, we developed a coreshell synthesis in which the Ge metalattice is protected by an oxide-free Si interfacial layer, and we explore its properties by transmission electron microscopy (TEM), Raman spectroscopy, and electron energy loss spectroscopy (EELS). The interstices of a colloidal crystal film grown from 69 nm diameter spherical silica particles were filled with polycrystalline Ge by high-pressure confined chemical vapor deposition (HPcCVD) from GeH4. After the SiO2 template was etched away with aqueous HF, the Ge replica was uniformly coated with an amorphous Si shell by HPcCVD as confirmed by TEM-EDS (energy-dispersive X-ray spectroscopy) and Raman spectroscopy. Formation of the shell prevents oxidation of the Ge core within the detection limit of XPS. The electronic properties of the core-shell structure were studied by accessing the Ge 3d edge onset using STEM-EELS. A blue shift in the edge onset with decreasing size of Ge sites in the metalattices suggests quantum confinement of the Ge core. The degree of quantum confinement of the Ge core depends on the void sizes in the template, which is tunable by using silica particles of varying size. The edge onset also shows a shift to higher energy near the shell in comparison with the Ge core. This shift along with the observation of Ge-Si vibrational modes in the Raman spectrum indicate interdiffusion of Ge and Si. Both the size of the voids in the template and core-shell interdiffusion of Si and Ge can in principle be tuned to modify the electronic properties of the Ge metalattice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Optimizing performance and yield of vertical GaN diodes using wafer scale optical techniques

Abstract To improve the manufacturing of vertical GaN devices for power electronics applications, the effects of defects in GaN substrates need to be better understood. Many non-destructive techniques including photoluminescence, Raman spectroscopy and optical profilometry, can be used to detect defects in the substrate and epitaxial layers. Raman spectroscopy was used to identify points of high crystal stress and non-uniform conductivity in a substrate, while optical profilometry was used to identify bumps and pits in a substrate which could cause catastrophic device failures. The effect of the defects was studied using vertical P-i-N diodes with a single zone junction termination extention (JTE) edge termination and isolation, which were formed via nitrogen implantation. Diodes were fabricated on and off of sample abnormalities to study their effects. From electrical measurements, it was discovered that the devices could consistently block voltages over 1000 V (near the theoretical value of the epitaxial layer design), and the forward bias behavior could consistently produce on-resistance below 2 mΩ cm 2 , which is an excellent value considering DC biasing was used and no substrate thinning was performed. It was found that high crystal stress increased the probability of device failure from 6 to 20%, while an inhomogeneous carrier concentration had little effect on reverse bias behavior, and slightly (~ 3%) increased the on-resistance (R on ). Optical profilometry was able to detect regions of high surface roughness, bumps, and pits; in which, the majority of the defects detected were benign. However a large bump in the termination region of the JTE or a deep pit can induce a low voltage catastrophic failure, and increased crystal stress detected by the Raman correlated to the optical profilometry with associated surface topography.

42 ENGINEERING↗
DOE OSTI2020

Selectively accessing the hotspots of optical nanoantennas by self-aligned dry laser ablation

Plasmonic nanostructures serve as optical antennas for concentrating the energy of incoming light in localized hotspots close to their surface. By positioning nanoemitters in the antenna hotspots, energy transfer is enabled, leading to novel hybrid antenna-emitter-systems, where the antenna can be used to manipulate the optical properties of the nano-objects. The challenge remains how to precisely position emitters within the hotspots. We report a self-aligned process based on dry laser ablation of a calixarene that enables the attachment of molecules within the electromagnetic hotspots at the tips of gold nanocones. Within the laser focus, the ablation threshold is exceeded in nanoscale volumes, leading to selective access of the hotspot areas. A first indication of the site-selective functionalization process is given by attaching fluorescently labelled proteins to the nanocones. In a second example, Raman-active molecules are selectively attached only to nanocones that were previously exposed in the laser focus, which is verified by surface enhanced Raman spectroscopy. Enabling selective functionalization is an important prerequisite e.g. for preparing single photon sources for quantum optical technologies, or multiplexed Raman sensing platforms.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Spatially resolved multimodal vibrational spectroscopy under high pressures

In this perspective, we discuss the potential impact on in situ studies under controlled environments of a novel multimodal spectroscopic technique, optical photothermal infrared + Raman spectroscopy, which enables the simultaneous collection of infrared and Raman scattering spectra, along with hyperspectral imaging and chemical imaging with wavelength-independent sub-500 nm spatial resolution. A brief review of the current literature regarding the O-PTIR technique is presented along with recent work from our own lab on determining the crystallinity of soft and inorganic materials. The results highlight the possibility of resolving differences in the crystallinity of soft materials associated with changes in material processing. Here, we also demonstrate the first reported use of a diamond anvil cell with simultaneous infrared and Raman measurements that showcases, using a high energy material as an example, the potential use of O-PTIR spectroscopy in diamond anvil cell techniques.

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

Thermal decomposition of neptunyl ammonium nitrate: mechanistic insights and structural characterization of the Np 2 O 5 intermediate phase

Neptunium (Np) possesses a rich and unique chemistry that often diverges from other actinide elements yet remains relatively underexplored compared with the other light actinides. A resurgence of interest in Np has been spurred by the application of 237 Np for plutonium-238 ( 238 Pu) production for use in radioisotope thermoelectric generators (RTGs), necessitating evaluation of Np chemical reactions and materials. The work presented here studied the thermal decomposition of neptunyl ammonium nitrate (NH 4 Np VI O 2 (NO 3 ) 3 ) for synthesis of neptunium dioxide (NpO 2 ), which is the target material used for production of 238 Pu. Additionally, structural characterization of the intermediate solid Np pentoxide (Np 2 O 5 ) was performed. Advanced solid-state characterization techniques, including simultaneous thermal analysis (STA), powder X-ray diffraction (pXRD), Raman spectroscopy, and density functional theory (DFT) modeling have been combined to study the reaction pathways. Analysis revealed that NH 4 Np VI O 2 (NO 3 ) 3 thermally decomposes to a proposed neptunyl nitrate intermediate, followed by Np 2 O 5 and finally NpO 2 , all within the temperature range of 150 °C–600 °C. Further characterization of the pentoxide intermediate provided the first Raman spectra of pure-phase Np 2 O 5 and associated DFT modeling confirmed Raman peak assignments for this phase. These findings provide mechanistic information to advance production of the critical radioisotope 238 Pu and advance the state of knowledge on Np materials chemistry using modern characterization techniques.

Lawson, Kathryn M. [Oak Ridge National Laboratory ↗
DOE OSTI2026

Modern insights into the mechanisms of neptunium oxalate decomposition

Neptunium oxalate (Np(C 2 O 4 ) 2 ·6H 2 O) is a historically relevant solid phase used in nuclear processing as a precursor for neptunium dioxide (NpO 2 ). Although Np oxalate has been synthesized and used for NpO 2 production for decades, the thermal decomposition mechanism of this phase remains poorly understood and has not been evaluated in over 30 years. Conflicting reports in historical literature suggest either a direct conversion from anhydrous oxalate to NpO 2 or a decomposition that includes the formation of Np carbonate or oxidized Np intermediate phases. In this work, we reexamine the decomposition pathway of Np(C 2 O 4 ) 2 ·6H 2 O using thermal analysis coupled with evolved gas analysis and temperature-dependent Raman spectroscopy to elucidate decomposition mechanisms and intermediate phases using modern analytical techniques. Thermal analysis revealed a three-stage decomposition process, including dehydration below 200 °C, oxalate breakdown between 170 and 370 °C, and NpO 2 formation by 500 °C. However, an unidentified plateau in the thermal data was observed during measurements. Raman spectroscopy confirmed the stages of decomposition, and in the analysis of potential intermediate phases, no carbonate phases or Np 2 O 5 were identified. Raman data suggest that residual oxalate or nonstoichiometric oxide are present during decomposition before pure NpO 2 is formed. These findings clarify aspects of the Np oxalate decomposition mechanism and address longstanding discrepancies in the literature, with a specific focus on Np-specific materials chemistry.

Lawson, Kathryn M. [Oak Ridge National Laboratory ↗
DOE OSTI2026

Spectro-Microscopic Analysis of Soot Particle Composition and Source Attribution

Ambient soot particles significantly impact Earth’s radiative balance, human health, and atmospheric visibility. Their microstructural properties depend on formation and aging mechanisms, which vary by emission source and atmospheric processes. Hence, accurately identifying sources of soot enhances our understanding of their physicochemical properties and atmospheric implications. This study used a multi-modal approach to characterize and attribute sources of submicron soot particles collected in Israel during new particle formation events, biomass burning episodes, and background atmospheric conditions. Synchrotron-based X-ray microscopy was used to map soot (elemental carbon), organic carbon, and inorganic species. Implemented atomic force microscopy showed highly diverse phase states, with soot consistently exhibiting a solid-like phase. Automated µ-Raman analysis was subsequently performed on ~690 particles, identifying three soot classes based on spectral features corresponding to the "Defect" (D) and "Graphite" (G) bands of soot. We applied two-peak and five-peak fitting approaches to deconvolute the “Defect” peaks (D1, D2, D3, and D4) and G band from average Raman, revealing varying degrees of graphitic order. The degree of graphitic order was determined from metrics such as the D3 peak area, often observed when soot was internally mixed with organic material. Raman spectral features, along with temporal variations in particle classes contributions, suggest that Particle Type 1 corresponds to traffic related soot and Particle Type 2 to less graphitic soot from biomass burning, while Particle Type 3 is associated with more heterogeneous particulate representative of soot-OC mixtures emitted during new particle formation and biomass burning episodes.

Rivera-Adorno, Felipe (ORCID:0000000273557999)↗
DOE OSTI2022

Vibrational modes and crystallographic structure of Cd 3 As 2 and (Cd 1-x Zn x ) 3 As 2 epilayers

Low-temperature Raman scattering is used to study the crystal structure of molecular-beam epitaxially grown layers of the Dirac semimetal Cd 3 As 2 and its related alloy (Cd 1-x Zn x ) 3 As 2 . The combination of narrow-linewidth spectra, multiple growth directions and full polarization analysis allows improved accuracy in identifying the irreducible representation of over 57 Raman-active vibrations. Several disagreements with previous identifications are found. Structurally, the results agree with the centrosymmetric I41/acd space group of bulk-grown Cd 3 As 2 and are clearly distinct from the Raman spectra of nanoscale platelets and wires. Three-fold twinning is seen in (112) Cd 3 As 2 grown on (111) zincblende substrates corresponding to the three possible tetragonal orientations. In dilute (Cd 1-x Zn x ) 3 As 2 , phonons have a frequency and scattering amplitude dependence on Zn concentration that is continuous with Cd 3 As 2 but at least one frequency is absent at the alloy endpoint, preventing a simple one-mode description of the alloy phonon.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A robust plasma-based laser amplifier via stimulated Brillouin scattering

Brillouin amplification in plasma is more resilient to fluctuations in the laser and plasma parameters than Raman amplification, making it an attractive alternative to Raman amplification. In this work, we focus on high plasma densities, n 0 > n cr /4, where stimulated Raman scattering is not possible and laser beam filamentation is the dominant competing process. Through analytic theory and multi-dimensional particle-in-cell simulations, we identify a parameter regime for which Brillouin amplification can be efficient while maintaining filamentation of the probe at a controlled level. We demonstrate pump-to-probe compression ratios of up to 72 and peak amplified probe fluences over 1 kJ cm -2 with ≃50% efficiency. High pulse quality is maintained through control of parasitic filamentation, enabling operation at large beam diameters. Provided the pump and probe pulse diameters can be increased to 1 mm, our results suggest that Brillouin amplification can be used to produce sub-picosecond pulses of petawatt power.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Pressure-driven symmetry transitions in dense H 2 O ice

X-ray diffraction and Raman spectroscopy of H 2 O (ice) structures are measured under static compression in combination with grain normalizing heat treatment via direct laser heating. Here, we report the transition from cubic ice-VII to a structure of tetragonal symmetry, ice-VII t at 5.1 ± 0.5 GPa. This is succeeded by the H-bond symmetrization transition occurring at a pressure of 30.9 ± 3 GPa. Both experimental observations are supported by simulated Raman spectra from density-functional theory quantum calculations. The transition to H-bond symmetrization is evidenced by the reversible emergence of its characteristic Raman mode and a 2.5-fold increase in bulk modulus, implying a significant increase in bonding strength.

58 GEOSCIENCES↗
DOE OSTI2019

Lattice dynamics and phase transitions in Fe 3 - x GeTe 2

We present Raman spectroscopy measurements of the van der Waals bonded ferromagnet Fe 3-x GeTe 2 , together with lattice dynamics. Four out of eight Raman active modes are observed and assigned, in agreement with numerical calculations. The energies and linewidths of the observed modes display an unconventional temperature dependence at about 150 and 220 K, followed by the nonmonotonic evolution of the Raman continuum. Whereas the former can be related to the magnetic phase transition, the origin of the latter anomaly remains an open question.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Coupling of organic cation and inorganic lattice in methylammonium lead halide perovskites: Insights into a pressure-induced isostructural phase transition

Organic-inorganic hybrid metal-halide perovskite (OIHP) materials provide a tunable platform for engineering their optoelectronic properties. Although several high-pressure studies have been conducted from the OIHP family of single crystals and films, the exact nature of the dynamic coupling of the CH 3 NH 3 (MA) cation with the octahedral lattice framework and the mechanisms responsible for the structural phase transformation under pressure are not well captured. By combined photoluminescence (PL), synchrotron-based x-ray diffraction, and Raman-scattering studies as a function of pressure from methylammonium lead bromide (MAPbBr 3 ), we shed light on an isostructural phase transition due to the coupling of the MA cation and the PbBr 6 lattice through hydrogen bonding. The sharp discontinuities at ~ 1 GPa and ~ 3 GPa in the PL peak positions correlate with the structural changes observed in high-pressure XRD and Raman-scattering studies. The electronic band edge as a function of pressure is calculated within density-functional theory. The PL peak position, intensity and width of the excitonic peak show significant changes at 2 GPa, which corroborate the changes observed in high-pressure Raman-scattering studies. The frequencies of the lattice modes and the C-H/N-H bending and stretching modes of the MA cation show anomalous changes and other nuances at 2 GPa. The suppression of rotational and orientational disorder of the organic moiety is initiated at 2 GPa and the ordering is completed by 3.0 GPa, leading to an order-disorder type cubic II (Im$\overline{3}$) to orthorhombic ( Pnma ) phase transition. Along with the revelation of an isostructural transformation at 2 GPa, this paper highlights the impact of molecular vibrations on the electronic properties of MAPbBr 3 under pressure.

36 MATERIALS SCIENCE↗
DOE OSTI2023

A comparative study of cerium oxides formed by pulsed laser ablation and continuous wave laser heating

Abstract The formation of Ce 2 O 3 from cerium metal requires complex reducing conditions. Alternatively, we show that different stoichiometries and structures of cerium oxides can be generated in high‐temperature laser experiments by varying the availability of oxygen and the use of either pulsed laser ablation (PLA) or continuous wave (CW) laser heating of cerium metal. X‐ray diffraction and Raman spectroscopy suggest that a low structural order Ce 2 O 3 /CeO 2 mixed structure is formed in a 1% O 2 atmosphere with PLA. For CW heating in a 1% O 2 environment, Raman measurements show the formation of crystalline A‐type Ce 2 O 3 in proximity to the point of laser impingement. These experiments were repeated in 18 O 2 and allowed us to report for the first time the corresponding Raman spectrum of Ce 2 18 O 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Quantitative far-infrared band strengths of iodine monochloride (ICl), a molten salt off-gas product

The gaseous (by)products generated from molten salt reactors need to be monitored to prevent the release of potentially toxic gases to the environment. In particular, 129I has a long half-life and its toxicity and persistence in the environment make iodine and iodine-containing compounds (such as ICl from chloride containing molten salt systems) of great concern. Optical spectroscopy tools, including Raman and Fourier-transform infrared (FTIR) spectroscopies, are ideal for monitoring and quantifying such off-gas products. Iodine (I2) has a strong and distinct Raman signature and the change in signal with a change in concentration can be used for quantification of these byproducts. Iodine monochloride (ICl) has distinct signatures in both the Raman and the infrared, and its spectrum can also potentially be used for quantitative measurement of this species. In this paper we discuss our recent results on the quantification of iodine monochloride using infrared spectroscopy, in particular first reports of the absolute infrared band strength of ICl.

infrared (IR) spectroscopy, Molten Salt Reactors, ↗
DOE OSTI2020

Nitrogen in black phosphorus structure

Group V elements in crystal structure isostructural to black phosphorus with unique puckered two-dimensional layers exhibit exciting physical and chemical phenomena. However, as the first element of group V, nitrogen has never been found in the black phosphorus structure. Here, we report the synthesis of the black phosphorus–structured nitrogen at 146 GPa and 2200 K. Metastable black phosphorus–structured nitrogen was retained after quenching it to room temperature under compression and characterized in situ during decompression to 48 GPa, using synchrotron x-ray diffraction and Raman spectroscopy. We show that the original molecular nitrogen is transformed into extended single-bonded structure through gauche and trans conformations. Raman spectroscopy shows that black phosphorus–structured nitrogen is strongly anisotropic and exhibits high Raman intensities in two A g normal modes. Synthesis of black phosphorus–structured nitrogen provides a firm base for exploring new type of high-energy-density nitrogen and a new direction of two-dimensional nitrogen.

58 GEOSCIENCES↗