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At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Noncollinear polar magnet Fe 2 (SeO 3 ) 3 (H 2 O) 3 with inequivalent Fe 3+ sites

The emergence of novel magnetic states becomes more likely when the inversion symmetry of the crystal field, relative to the center between two spins, is broken. We propose that placing magnetic spins in inequivalent sites in a polar lattice can promote a realization of nontrivial magnetic states and associated magnetic properties. To test our hypothesis, we study Fe 2 (SeO 3 )(H 2 O) 3 as a model system that displays two distinct Fe(1) and Fe(2) magnetic sites in a polar structure (R3c space group). At low fields μ 0 H≤ 0.06 T, the material undergoes an antiferromagnetic ordering with T N1 = 77 K and a second transition at T N2 ≈ 4 K. At μ 0 H≥ 0.06 T and 74 K ≤T≤ 76 K, a positive entropy change of ∼0.12 mJ mol −1 K −1 can be associated with a metamagnetic transition to possibly nontrivial spin states. At zero field, Fe(1) is nearly fully ordered at T≈ 25 K, while Fe(2) features magnetic frustration down to T = 4 K. The magnetic ground state, a result corroborated by single-crystal neutron diffraction and 57 Fe Mössbauer spectroscopy, is a noncollinear antiparallel arrangement of ferrimagnetic Fe(1)–Fe(2) dimers along the c-axis. The results demonstrate that placing distinct magnetic sites in a polar crystal lattice can enable a new pathway to modifying spin, orbital, and lattice degrees of freedom for unconventional magnetism.

Crystal lattices↗
DOE OSTI2023

Photoluminescence spectroscopy of Cr 3+ in β-Ga 2 O 3 and (Al 0.1 Ga 0.9 ) 2 O 3

Alloying β-Ga 2 O 3 with Al 2 O 3 to create (Al x Ga 1–x ) 2 O 3 enables ultra-wide bandgap materials suitable for applications deep into ultraviolet. In this work, photoluminescence (PL) spectra of Cr 3+ were investigated in monoclinic single crystal β-Ga 2 O 3 , and 10 = mol. % Al 2 O 3 alloyed with β-Ga 2 O 3 , denoted β-(Al 0.1 Ga 0.9 ) 2 O 3 or AGO. Temperature-dependent PL properties were studied for Cr 3+ in AGO and β-Ga 2 O 3 from 295 to 16 K. For both materials at room temperature, the red-line emission doublet R 1 and R 2 occurs at 696 nm (1.78 eV) and 690 nm (1.80 eV), respectively, along with a broad emission band at 709 nm (1.75 eV). Here, the linewidths for AGO are larger for all temperatures due to alloy broadening. For both materials, the R-lines blue-shift with decreasing temperature. The (lowest energy) R 1 line is dominant at low temperatures due to the thermal population of the levels. For temperatures above ~50 K, however, the ratio of R 2 to R 1 peak areas is dominated by nonradiative combination.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Wafer-Scale Synthesis of 2D Materials by an Amorphous Phase-Mediated Crystallization Approach

The interest in the wafer-scale growth of two-dimensional (2D) materials, including transition metal dichalcogenides (TMDCs), has been rising for transitioning from lab-scale devices to commercial-scale systems. Among various synthesis techniques, physical vapor deposition, such as pulsed laser deposition (PLD), has shown promise for the wafer-scale growth of 2D materials. However, due to the high volatility of chalcogen atoms (e.g., S and Se), films deposited by PLD usually suffer from a lack of stoichiometry and chalcogen deficiency. To mitigate this issue, excess chalcogen is necessary during the deposition, which results in problems like uniformity or not being repeatable. This study demonstrates a condensed-phase or amorphous phase-mediated crystallization (APMC) approach for the wafer-scale synthesis of 2D materials. This method uses a room-temperature PLD process for the deposition and formation of amorphous precursors with controlled thicknesses, followed by a post-deposition crystallization process to convert the amorphous materials to crystalline structures. This approach maintains the stoichiometry of the deposited materials throughout the deposition and crystallization process and enables the large-scale synthesis of crystalline 2D materials (e.g., MoS 2 and WSe 2 ) on Si/SiO 2 substrates, which is critical for future wafer-scale electronics. We show that the thickness of the layers can be digitally controlled by the number of laser pulses during the PLD phase. Optical spectroscopy is used to monitor the crystallization dynamics of amorphous layers as a function of annealing temperature. The crystalline quality, domain sizes, and the number of layers were explored using nanoscale and atomistic characterization (e.g., AFM, STEM, and EDS) along with electrical characterization to explore process–structure–performance relationships. Finally, this growth technique is a promising method that could potentially be adopted in conventional semiconductor industries for wafer-scale manufacturing of next-generation electronic and optoelectronic devices.

2D electronics↗
DOE OSTI2025

Investigation of Americium-Containing Phosphates, Silicates, Borates, Molybdates, and Fluorides Synthesized via High-Temperature Flux Crystal Growth

The crystal chemistry of americium-containing extended structures was investigated, and several classes of americium-containing solid-state oxide materials were obtained in single-crystal form via high-temperature flux crystal growth. This enabled the structural characterization of rare examples of ternary, quaternary, and penternary americium-containing silicates K 3 Am (Si 2 O 7 ) and Cs 6 Am 2 Si 21 O 48 , phosphates Na 3 Am (PO 4 ) 2 and K 3 Am (PO 4 ) 2 , borates Ba 3 Am 2 (BO 3 ) 4 and AmBO 3 , borate halides Ca 5 Am(BO 3 ) 4 Cl, molybdates Li 0.5 Am 0.5 MoO 4 , and fluorides CsAm 2 F 7 . Using these crystallographic data, the ionic radii of Am 3+ with coordination numbers of six (0.975 Å), seven (1.052 Å), and nine (1.162 Å) were established. A maximum entropy method (MEM) analysis was performed on the single-crystal X-ray diffraction data that were collected for K 3 Nd(PO 4 ) 2 /K 3 Am(PO 4 ) 2 , K 3 NdSi 2 O 7 /K 3 AmSi 2 O 7 , and NdBO 3 /AmBO 3 , to qualitatively compare the ionicities of the Nd–O and Am–O bonds. In conclusion, Raman spectroscopy data were collected on single crystals of K 3 Am(PO 4 ) 2 and compared to the calculated Raman spectrum of K 3 Am(PO 4 ) 2 obtained from DFT calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Solid state reduction of nickelate thin films

The square-planar nickelates are a class of superconductors analogous to the cuprates and promise to provide insight into the pairing mechanism in high-temperature superconducting oxides. The parent phase of doped superconducting films is NdNiO 2 , which is prepared by reducing 3 + Ni in NdNiO 3 films. In this paper, we develop an ultrahigh vacuum reduction method using aluminum deposited on top of the 3 + nickelates and monitor the reduction process in real time through in situ crystal truncation rod measurements and diffraction x-ray absorption near edge spectroscopy measurements across the Ni K edge. Further, we establish a relation between Ni valence and the lattice constant of NdNiO 3-x and show that the process can precisely control the oxygen content in the films. Finally, we extend the reduction process to quintuple square-planar nickelates.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Effects of organic additives on calcium hydroxide crystallisation during lime slaking

Highlights: • Sucrose and lignosulfonate reduce the crystallite size of Ca(OH){sub 2}. • Lime slaking in sucrose solutions leads to Ca(OH)2 with irregular shape. • Lime slaking in presence of lignosulfonate leads to plate-like Ca(OH){sub 2} crystals. • Effects of additives are enhanced when introduced before slaking. • Additives stabilise the unstable edge faces of Ca(OH){sub 2} during ageing. Organic compounds, often used in cement systems as admixtures, may affect the crystallisation and carbonation kinetics of Ca(OH){sub 2}, an important phase of hydrated cement. Here, we investigated changes in Ca(OH){sub 2} morphology in the presence of 3 organic compounds, commonly encountered in cement and lime-based materials: sucrose, pectin and calcium lignosulfonate. The additives were introduced either before or after lime slaking to determine the influence of temperature. Ca(OH){sub 2} crystals and supernatant solutions were characterised at time of slaking and after 6 months of ageing using scanning electron microscopy, X-ray diffraction and optical emission spectroscopy. Our results indicate that the morphology of Ca(OH){sub 2} crystals is modified by the characteristics of the organic molecules which promote formation of Ca(OH){sub 2} with habits that can result in faster carbonation, an effect that is detrimental to cement used in reinforced concrete. These effects are enhanced when the additives are introduced before slaking, likely as a result of thermal degradation.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Enhanced domain dynamics in alternating current poled rhombohedral Pb(Mg 1/3 Nb 2/3 )O 3 –PbTiO 3 single crystals

Abstract The understanding of domain dynamics in ferroelectric materials is crucial for optimizing their performance in piezoelectric and electro‐optic applications. Although previous studies have focused on static domain structures and macroscopic characteristics, the time‐resolved approach of domains remains largely unexplored. In this study, we compare the dynamic responses of direct current (DC) and alternating current (AC) poled [001]‐oriented rhombohedral Pb(Mg 1/3 Nb 2/3 )O 3 –PbTiO 3 (PMN–PT) single crystals using X‐ray photon correlation spectroscopy (XPCS) during the application of external electric fields. Our results demonstrate that the AC‐poled sample exhibit enhanced reconfiguration of domain variants in response to driving fields compared to the DC‐poled counterpart, as evidenced by accelerated correlation decay and faster relaxation time. This phenomenon is attributed to enhanced reversible domain wall motion achieved through AC poling, which facilitates field‐induced domain realignment. These findings provide insight into the relationship between dynamics and macroscopic properties in relaxor‐PT single crystals for high‐performance applications.

36 MATERIALS SCIENCE↗
DOE OSTI2025

To thread or not to thread: Reaction of uranyl (UO 2 2+ ) with two Aza-crown macrocycles

The complexation of the uranyl ion (UO 2 2+ ) by macrocyclic ligands is hindered by the rigidly enforced trans orientation of its oxo ligands. To further investigate this coordination chemistry challenge, here we investigate the reactivity of UO 2 2+ with two different 18-membered aza-crown macrocycles, diaza-dibenzo-18-crown-6 (DADBC) and 7,16-bis(N-methylacetamide)diaza-18-crown-6 (BAM). The reaction of uranyl triflate, [UO 2 (OTf) 2 (THF) 3 ], with DADBC in toluene afforded [UO 2 (DADBC)][OTf] 2 , in which the UO 2 2+ ion is fully encapsulated by the macrocycle. This conclusion was supported by NMR, UV–Vis, IR, and Raman spectroscopies, as well as single-crystal X-ray crystallography. Attempts to form the in-macrocycle complex of BAM, however, were unsuccessful. Here, the reaction of BAM with [UO 2 (OTf) 2 (THF) 3 ] in THF/CH 2 Cl 2 unexpectedly afforded crystals of [H 2 BAM][OTf] 2 , where the protons are derived from solvate water in the BAM crystal lattice.

Actinide↗
DOE OSTI2021

Structural and vibrational properties of methane up to 71 GPa

Single-crystal synchrotron x-ray diffraction, Raman spectroscopy, and first principles calculations have been used to identify the structure of the high-pressure (HP) phase of molecular methane above 20 GPa up to 71 GPa at room temperature. The structure of the HP phase is trigonal R3, which can be represented as a distortion of the cubic phase B, previously documented at 7–15 GPa and confirmed here. The positions of hydrogen atoms in the HP phase have been obtained from first principles calculations, which also demonstrated the stability of this structure above 260 K at 25 GPa. The molecules occupy four different crystallographic sites in phase B and 11 sites in the HP phase, which result in splitting of molecular stretching modes detected in Raman spectroscopy and assigned here based on a good agreement with the Raman spectra calculated from the first principles. Furthermore, our study points out to a single HP phase unlike up to three HP phases proposed previously based on the Raman spectroscopy results only.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

TlSr 2 I 5 :Eu 2+ - A new high density scintillator for gamma-ray detection

In this paper we report on the scintillation properties of TlSr 2 I 5 doped with Eu 2+ , a novel thallium-containing high-resolution scintillator for gamma-ray spectroscopy. Here, small diameter, good quality crystals of TlSr 2 I 5 :Eu (TSI) with different Eu 2+ concentrations were grown by the vertical Bridgman method. X-ray diffraction measurements show that single crystals of TSI belong to the monoclinic system with space group P2 1 /c. TlSr 2 I 5 has a density of 5.32 g/cm 3 and effective Z of 60. The X-ray excited emission of Eu 2+ doped TlSr 2 I 5 features a broad emission band peaking between 460–470 nm. The light yield of TlSr 2 I 5 crystal doped with 1% Eu 2+ is measured to be ~72,000 ph/MeV with an energy resolution of 2.8% at 662 keV. The scintillation decay time which is characteristic of Eu 2+ shows two components, with 90% of the light in a ~500 ns component and the rest in a longer component of ~3 μs.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2024

Optical tuning of the diamond Fermi level measured by correlated scanning probe microscopy and quantum defect spectroscopy

Quantum technologies based on quantum point defects in crystals require control over the defect charge state. Here we tune the charge state of shallow nitrogen-vacancy and silicon-vacancy centers by locally oxidizing a hydrogenated surface with moderate optical excitation and simultaneous spectral monitoring. The loss of conductivity and change in work function due to oxidation are measured in atmosphere using conductive atomic force microscopy and Kelvin probe force microscopy (KPFM). We correlate these scanning probe measurements with optical spectroscopy of the nitrogen-vacancy and silicon-vacancy centers created via implantation 15–25 nm beneath the diamond surface and annealing. The observed charge state of the defects as a function of optical exposure demonstrates that laser oxidation provides a way to precisely tune the Fermi level over a range of at least 2.00 eV. We also observe a significantly larger oxidation rate for implanted surfaces compared to unimplanted surfaces under ambient conditions. Here, combined with knowledge of the electron affinity of a surface, these results suggest KPFM is a powerful, high-spatial-resolution technique to advance surface Fermi level engineering for charge stabilization of quantum defects.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Magnetosynthesis effect on magnetic order, phonons, and magnons in single-crystal Sr 2 ⁢ IrO 4

It was shown earlier that applying a magnetic field during the growth of Sr 2 IrO 4 , also known as “field-alteration”, induces significant changes to its structural, magnetic, and transport properties. However, the microscopic nature of these changes is enigmatic. Here, in this study, we employed resonant elastic and inelastic x-ray scattering, as well as Raman scattering, to investigate samples from two batches of Sr 2 IrO 4 grown in magnetic fields of different strengths. Our findings reveal that samples grown in a weaker magnetic field have similar magnetic order to non-altered samples, whereas those grown in a stronger field show a different stacking of weak in-plane ferromagnetic moments. Additionally, we observed significant softening and broadening of select Raman-active phonons in the field altered samples, with a stronger effect in the samples grown in the stronger field. We discuss insights that our results provide into the microscopic nature of field-alteration in Sr 2 IrO 4 .

36 MATERIALS SCIENCE↗
DOE OSTI2021

Patient mutations in human ATP:cob(I)alamin adenosyltransferase differentially affect its catalytic versus chaperone functions

Human ATP:cob(I)alamin adenosyltransferase (ATR) is a mitochondrial enzyme that catalyzes an adenosyl transfer to cob(I)alamin, synthesizing 5'-deoxyadenosylcobalamin (AdoCbl) or coenzyme B 12 . ATR is also a chaperone that escorts AdoCbl, transferring it to methylmalonyl-CoA mutase, which is important in propionate metabolism. Mutations in ATR lead to methylmalonic aciduria type B, an inborn error of B12 metabolism. Our previous studies have furnished insights into how ATR protein dynamics influence redox-linked cobalt coordination chemistry, controlling its catalytic versus chaperone functions. In this study, we have characterized three patient mutations at two conserved active site residues in human ATR, R190C/H, and E193K and obtained crystal structures of R190C and E193K variants, which display only subtle structural changes. All three mutations were found to weaken affinities for the cob(II)alamin substrate and the AdoCbl product and increase K M(ATP) . 31 P NMR studies show that binding of the triphosphate product, formed during the adenosylation reaction, is also weakened. However, although the k cat of this reaction is significantly diminished for the R190C/H mutants, it is comparable with the WT enzyme for the E193K variant, revealing the catalytic importance of Arg-190. Furthermore, although the E193K mutation selectively impairs the chaperone function by promoting product release into solution, its catalytic function might be unaffected at physiological ATP concentrations. In contrast, the R190C/H mutations affect both the catalytic and chaperoning activities of ATR. Because the E193K mutation spares the catalytic activity of ATR, our data suggest that the patients carrying this mutation are more likely to be responsive to cobalamin therapy.

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

Dynamics at the crystal-melt interface in a supercooled chalcogenide liquid near the glass transition

Direct quantitative measurements of nanoscale dynamical processes associated with structural relaxation and crystallization near the glass transition are a major experimental challenge. These type of processes have been primarily treated as macroscopic phenomena within the framework of phenomenological models and bulk experiments. Here, we report x-ray photon correlation spectroscopy measurements of dynamics at the crystal-melt interface during the radiation induced formation of Se nano-crystallites in pure Se and in binary AsSe 4 glass-forming liquids near their glass transition temperature. We observe a heterogeneous dynamical behaviour where the intensity correlation functions g 2 (q, t) exhibits either a compressed or a stretched exponential decay, depending on the size of the Se nano-crystallites. The corresponding relaxation timescale for the AsSe 4 liquid increases as the temperature is raised, which can be attributed to changes in the chemical composition of the melt at the crystal-melt interface with the growth of the Se nano-crystallites.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Formation of U(VI) peroxide nanoclusters from cascade reactions with a persulfate radical initiator

Radiolysis of water in high radiation fields generates a variety of reactive oxygen species that influence the chemical behavior and complexation of hexavalent uranium. This study investigates the behavior of interaction of a uranyl cation (UO 2 2+ (VI)) with a series of free radicals that are formed in situ via activation of the free radical initiator persulphate (S 2 O 8 2− ), which releases both SO 4 ˙ − and ˙OH species in the solution. Electron Paramagnetic Resonance (EPR) and Raman spectroscopy were used to evaluate the presence of the hydroperoxyl radical (HO 2 ˙) and superoxide radicals (O 2 ˙ − ) that are formed within the solution through radical cascade reactions. In addition, a uranyl peroxide cluster solid (NaU 24 ) was crystallized and characterized using single crystal X-ray diffraction (SCXRD), vibrational spectroscopy, and EPR spectroscopy. The presence of the hydroperoxyl radical (HO 2 ˙) and superoxide radicals (O 2 ˙ − ) was also observed in the solid-state compound, but spectroscopic evidence suggests that it was associated with the Na + network and not the cluster itself. Density functional theory (DFT) calculations were also utilized to further confirm the radical species produced and determine the potential stabilization of radicals detected within the cluster and lattice.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Thermodynamic and Kinetic Modulation of Methylammonium Lead Bromide Crystallization Revealed by In Situ Monitoring

Hybrid organic–inorganic perovskite (HOIP) crystals are promising optoelectronic materials, but little is known about either the thermodynamic and kinetic controls on crystal growth or the underlying growth mechanism(s). Herein, we use fluid cell atomic force microscopy (AFM) and solution nuclear magnetic resonance (NMR) spectroscopy to investigate growth of the model HOIP crystal CH 3 NH 3 PbBr 3 (MAPbBr 3 ) and to determine how formic acid (HCOOH) modulates the thermodynamics and kinetics of growth. The results show that growth of MAPbBr 3 in dimethylformamide (DMF) proceeds through the classical pathway by the spreading of atomic crystal steps generated at screw dislocations on the {100} surface. Temperature dependent step velocity measurements demonstrate that with increasing concentration, HCOOH decreases both the solubility of MAPbBr 3 and the kinetic coefficient (b) of step movement. 1 H-NMR measurements indicate that HCOOH increases the lifetime of the methylammonium (MA + ) ions and promotes the association of MAPbBr 3 , thus tuning the solubility of the perovskite. HCOOH also alters the molecular tumbling motion and bulk diffusion of the MA + ions, possibly via H-bonding. Further, our findings establish a direct correlation between the mesoscale crystal growth kinetics and the molecular-scale interactions between organic additives and constituent ions, providing unprecedented insights for developing predictive syntheses of HOIP crystals with defined size, crystal habit and shape, and defect distribution.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Characterization of stilbene-d 12 for neutron spectroscopy without time of flight

In this work, we have experimentally characterized the light-output response of a deuterated trans-stilbene (stilbene-d 12 ) crystal to quasi-monoenergetic neutrons in the 0.8 to 4.4 MeV energy range. These data allowed us to perform neutron spectroscopy measurements of a DT 14.1 MeV source and a 239 PuBe source by unfolding the impinging neutron spectrum from the measured light-output response. The stilbene-d 12 outperforms a 1 H-stilbene of similar size when comparing the shape of the unfolded spectra and the reference ones. These results confirm the viability of non-hygroscopic stilbene-d 12 crystal for direct neutron spectroscopy without need for time-of-flight measurements. This capability makes stilbene-d 12 a well suited detector for fast-neutron spectroscopy in many applications including nuclear reaction studies, radiation protection, nuclear non-proliferation, and space travel.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗