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At least 649 records · Page 36
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Phonon dynamics and Urbach energy studies of MgZnO alloys

The Mg{sub x}Zn{sub 1−x}O alloy system is emerging as an environmentally friendly choice in ultraviolet lighting and sensor technologies. Knowledge of defects which impact their optical and material properties is a key issue for utilization of these alloys in various technologies. The impact of phase segregation, structural imperfections, and alloy inhomogeneities on the phonon dynamics and electronic states of Mg{sub x}Zn{sub 1−x}O thin films were studied via selective resonant Raman scattering (SRRS) and Urbach analyses, respectively. A series of samples with Mg composition from 0–68% were grown using a sputtering technique, and the optical gaps were found to span a wide UV range of 3.2–5.8 eV. The extent of the inherent phase segregation was determined via SRRS using two UV-laser lines to achieve resonance with the differing optical gaps of the embedded cubic and wurtzite structural domains. The occurrence of Raman scattering from cubic structures is discussed in terms of relaxation of the selection rules due to symmetry breaking by atomic substitutions. The Raman linewidth and Urbach energy behavior indicate the phase segregation region occurs in the range of 47–66% Mg. Below the phase segregation, the longitudinal optical phonons are found to follow the model of one-mode behavior. The phonon decay model of Balkanski et al. indicates that the major contributor to Raman linewidth arises from the temperature-independent term attributed to structural defects and alloy inhomogeneity, while the contribution from anharmonic decay is relatively small. Moreover, a good correlation between Urbach energy and Raman linewidth was found, implying that the underlying crystal dynamics affecting the phonons also affect the electronic states. Furthermore, for alloys with low Mg composition structural defects are dominant in determining the alloy properties, while at higher compositions alloy inhomogeneity cannot be neglected.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Purification of CdZnTe by electromigration

Electro-migration of ionized/electrically active impurities in CdZnTe (CZT) was successfully demonstrated at elevated temperature with an electric field of 20 V/mm. Copper, which exists in positively charged states, electro-migrated at a speed of 15 μm/h in an electric field of 20 V/mm. A notable variation in impurity concentration along the growth direction with the segregation tendency of the impurities was observed in an electro-migrated CZT boule. Notably, both Ga and Fe, which exist in positively charged states, exhibited the opposite distribution to that of their segregation tendency in Cd(Zn)Te. A CZT detector fabricated from the middle portion of the electro-migrated CZT boule showed an improved mobility-lifetime product of 0.91 × 10{sup −2} cm{sup 2}/V, compared with that of 1.4 × 10{sup −3} cm{sup 2}/V, observed in an as-grown (non-electro-migrated) CZT detector. The optimum radiation detector material would have minimum concentration of deep traps required for compensation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2013

CONSTRAINING INTERMEDIATE-MASS BLACK HOLES IN GLOBULAR CLUSTERS

Decades after the first predictions of intermediate-mass black holes (IMBHs) in globular clusters (GCs) there is still no unambiguous observational evidence for their existence. The most promising signatures for IMBHs are found in the cores of GCs, where the evidence now comes from the stellar velocity distribution, the surface density profile, and, for very deep observations, the mass-segregation profile near the cluster center. However, interpretation of the data, and, in particular, constraints on central IMBH masses, require the use of detailed cluster dynamical models. Here we present results from Monte Carlo cluster simulations of GCs that harbor IMBHs. As an example of application, we compare velocity dispersion, surface brightness and mass-segregation profiles with observations of the GC M10, and constrain the mass of a possible central IMBH in this cluster. We find that, although M10 does not seem to possess a cuspy surface density profile, the presence of an IMBH with a mass up to 0.75% of the total cluster mass, corresponding to about 600 M{sub Sun }, cannot be excluded. This is also in agreement with the surface brightness profile, although we find it to be less constraining, as it is dominated by the light of giants, causing it to fluctuate significantly. We also find that the mass-segregation profile cannot be used to discriminate between models with and without IMBH. The reason is that M10 is not yet dynamically evolved enough for the quenching of mass segregation to take effect. Finally, detecting a velocity dispersion cusp in clusters with central densities as low as in M10 is extremely challenging, and has to rely on only 20-40 bright stars. It is only when stars with masses down to 0.3 M{sub Sun} are included that the velocity cusp is sampled close enough to the IMBH for a significant increase above the core velocity dispersion to become detectable.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2016

Zoomed high-resolution simulations of Multi-coupled Dark Energy: cored galaxy density profiles at high redshift

We perform for the first time high-resolution zoom-in re-simulations of individual halos in the context of the Multi-coupled Dark Energy (McDE) scenario, which is characterised by the existence of two distinct Dark Matter particle species with opposite couplings to a Dark Energy scalar field. We compare the structural properties of the simulated halos to the standard ΛCDM results. The zoomed-in initial conditions are set up using a specifically designed code called ZInCo that we publicly release along with the present paper. Our numerical results allow to investigate in detail and with unprecedented resolution the halo segregation process that characterises McDE cosmologies from its very early stages. In particular, we find that in contrast to what could be inferred from previous numerical analysis at lower resolution, the segregation process is already in place at redshifts as high as z ∼ 7. Most remarkably, we find that the subsequent evolution of the segregation leads to the formation of cored total matter density profiles with a core size that progressively increases in time. The shape of the cored profiles can be accurately predicted as the superposition of two NFW profiles with an increasing offset, thereby confirming the interpretation of the simulations results in terms of the segregation of the two dark matter components of the halo as a consequence of their different coupling to the Dark Energy field.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2017

Diffusion and Clustering of Carbon Dioxide on Non-porous Amorphous Solid Water

Observations by ISO and Spitzer toward young stellar objects showed that CO{sub 2} segregates in the icy mantles covering dust grains. Thermal processing of the ice mixture was proposed as being responsible for the segregation. Although several laboratories studied thermally induced segregation, a satisfying quantification is still missing. We propose that the diffusion of CO{sub 2} along pores inside water ice is the key to quantify segregation. We combined Temperature Programmed Desorption and Reflection Absorption InfraRed Spectroscopy to study how CO{sub 2} molecules interact on a non-porous amorphous solid water (np-ASW) surface. We found that CO{sub 2} diffuses significantly on an np-ASW surface above 65 K and clusters are formed at well below one monolayer. A simple rate equation simulation finds that the diffusion energy barrier of CO{sub 2} on np-ASW is 2150 ± 50 K, assuming a diffusion pre-exponential factor of 10{sup 12} s{sup −1}. This energy should also apply to the diffusion of CO{sub 2} on the wall of pores. The binding energy of CO{sub 2} from CO{sub 2} clusters and CO{sub 2} from H{sub 2}O ice has been found to be 2415 ± 20 K and 2250 ± 20 K, respectively, assuming the same prefactor for desorption. CO{sub 2}–CO{sub 2} interaction is stronger than CO{sub 2}–H{sub 2}O interaction, in agreement with the experimental finding that CO{sub 2} does not wet the np-ASW surface. For comparison, we carried out similar experiments with CO on np-ASW, and found that the CO–CO interaction is always weaker than CO–H{sub 2}O. As a result, CO wets the np-ASW surface. This study should be of help to uncover the thermal history of CO{sub 2} on the icy mantles of dust grains.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

Understanding How Processing Additives Tune the Nanoscale Morphology of High Efficiency Organic Photovoltaic Blends: From Casting Solution to Spun-Cast Thin Film

Adding a small amount of a processing additive to the casting solution of photoactive organic blends has been demonstrated to be an effective method for achieving improved power conversion efficiency (PCE) in organic photovoltaics (OPVs). However, an understanding of the nano-structural evolution occurring in the transformation from casting solution to thin photoactive films is still lacking. In this report, the effects of the processing additive diiodooctane (DIO) on the morphology of the established blend of PBDTTT-C-T polymer and the fullerene derivative PC71BM used for OPVs are investigated, starting in the casting solution and tracing the effects in spun-cast thin films by using neutron/X-ray scattering, neutron reflectometry, and other characterization techniques. The results reveal that DIO has no observable effect on the structures of PBDTTT-C-T and PC71BM in solution; however, in the spun-cast films, it significantly promotes their molecular ordering and phase segregation, resulting in improved PCE. Thermodynamic analysis based on Flory-Huggins theory provides a rationale for the effects of DIO on different characteristics of phase segregation due to changes in concentration resulting from evaporation of the solvent and additive during film formation. Such information may help improve the rational design of ternary blends to more consistently achieve improved PCE for OPVs.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Origin of dislocation structures in an additively manufactured austenitic stainless steel 316L

In this experiment, the origin of dislocation structures in AM stainless steels was systematically investigated by controlling the effect of thermal stress through geometric constraints for the first time. Stainless steel 316L parts were produced in the form of “1D” rods, “2D” walls, and "3D" rectangular prisms to evaluate the effect of constraints to thermal expansion/shrinkage on the development of defect microstructures and to elucidate the origin of additively manufactured (AM) dislocation microstructures. Dislocation density, organization, chemical micro-segregation, precipitate structures, and misorientations were analyzed as a function of increasing constraints around solidifying material in 1D, 2D, and 3D components built using both directed energy deposition (DED) and powder-bed selective laser melting (SLM). In DED parts, the dislocation density was not dependent on local misorientations or micro-segregation patterns, but evolved from approximately ρ ⊥ = 10 12 m -2 in 1D parts to ρ ⊥ = 10 14 m -2 in 3D parts, indicating that it is primarily thermal distortions that produce AM dislocation structures. In DED 3D parts and SLM parts, dislocation densities were highest (ρ ⊥ ≈ 10 14 m -2 ) and corresponded to the formation of dislocation cells approximately 300-450 nm in diameter. Dislocation cells overlapped with dendrite micro-segregation in some but not all cases. The results illustrate that dendritic micro-segregation, precipitates, or local misorientations influence how the dislocations organize during processing, but are not responsible for producing the organized cell structures. Furthermore, this work shows that AM dislocation structures originate due to thermal distortions during printing, which are primarily dictated by constraints surrounding the melt pool and thermal cycling.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Reduced grain boundary energies in rare-earth doped MgAl 2 O 4 spinel and consequent grain growth inhibition

In this paper, grain growth inhibition in MgAl 2 O 4 spinel nanostructure was achieved by grain boundary (GB) segregation of rare-earth dopants. Microcalorimetric measurements showed that dense spinel compacts doped with 3 mol% of R 2 O 3 (R = Y, Gd, and La) had decreased GB energies as compared to the undoped spinel, representing reduction in the driving force for grain growth. Segregation energies of the three dopants to the Σ3 (111) GB were calculated by atomistic simulation. The dopants with higher ionic radius tend to segregate more strongly to GBs. The GB energies were calculated from atomistic simulation and, consistent with experiments, a systematic reduction in GB energy with dopant ionic size was found. Finally, high temperature grain growth experiments revealed a significant reduction of grain growth in the doped nanostructures as compared to the undoped one, which was attributed to increased metastability or possibly also a GB dragging originated from the dopant segregation.

36 MATERIALS SCIENCE↗
DOE OSTI2013

A Level Set Evaporation Model for Heterogeneous Atom Probe Tip

With the development of local electrode atom probe tomography (LEAP), the materials systems feasible for atomic structure determination has expanded from predominantly metals to include heterogeneous materials with complex structure and compositions. This makes the 3D atomic structure determination possible for most energy materials in battery, fuel cell, semiconductor, and nuclear applications. Atom probe tomography (APT) has been utilized to study multiphase materials with segregation and interface problems. The unique and quantitative information retrieved from APT can provide a foundation for the study of kinetic pathways, nanoscale composition mapping, multilayer interfacial segregation, dislocations and grain boundaries. However, a new challenge surfaces when the materials systems expand into heterogeneous materials: the traditional structure reconstruction introduces false magnification and large artifacts due to the underlying assumption of uniform and isotropic evaporation.

Atom probe, heterogeneous structure, evporation mo↗
DOE OSTI2026

Strain Relaxation and Relative Defect Density with Thickness in MBE-Grown Ge 0.85 Sn 0.15 on Ge(001)

Germanium–tin (GeSn) alloys are emerging as promising materials for mid-infrared optoelectronics and silicon-compatible photonic devices, owing to their tunable direct bandgap. However, the growth of high-quality GeSn films with high Sn content remains challenging due to strain-induced defect formation. In this study, we investigate the role of film thickness on strain-induced relaxation, defect density, and Sn segregation. A series of five samples with varying thicknesses and ∼15% Sn-containing GeSn layers were grown, ranging from the critical thickness for strain relaxation to the onset of Sn segregation. All GeSn samples were analyzed using X-ray diffraction reciprocal space mapping (XRD-RSM) to explore the evolution of strain-induced relaxation as a function of thickness. Photoluminescence measurements reveal that increasing the GeSn thickness enhances strain relaxation while reducing defect-related emission, indicating a decrease in effective defect density prior to reaching the threshold thickness of GeSn layer. At a thickness of ∼150 nm, the GeSn layer shows the onset of Sn segregation, evident in the XRD-RSM spectrum, marking the threshold thickness for Sn segregation. This work defines an effective growth window in terms of thickness (35 to 150 nm) for fabricating relaxed, defect-suppressed GeSn layers with 15% Sn content. These findings emphasize the crucial role of thickness control in balancing strain relaxation and defect suppression, advancing the fabrication of high-quality, high Sn-content relaxed GeSn using molecular beam epitaxy.

Defects↗
DOE OSTI2016

Improving the Thermodynamic Stability of Aluminate Spinel Nanoparticles with Rare Earths

Surface energy is a key parameter to understand and predict the stability of catalysts. In this work, the surface energy of MgAl 2 O 4 , an important base material for catalyst support, was reduced by using dopants prone to form surface excess (surface segregation): Y 3+ , Gd 3+ , and La 3+ . The energy reduction was predicted by atomistic simulations of spinel surfaces and experimentally demonstrated by using microcalorimetry. The surface energy of undoped MgAl 2 O 4 was directly measured as 1.65 ± 0.04 J/m 2 and was reduced by adding 2 mol % of the dopants to 1.55 ± 0.04 J/m 2 for Y-doping, 1.45 ± 0.05 J/m 2 for Gd-doping, and 1.26 ± 0.06 J/m 2 for La-doping. Atomistic simulations are qualitatively consistent with the experiments, reinforcing the link between the role of dopants in stabilizing the surface and the energy of segregation. Surface segregation was experimentally assessed using electron energy loss spectroscopy mapping in a scanning transmission electron microscopy image. Finally, the reduced energy resulted in coarsening inhibition for the doped samples and, hence, systematically smaller particle sizes (larger surface areas), meaning increased stability for catalytic applications. Moreover, both experiment and modeling reveal preferential dopant segregation to specific surfaces, which leads to the preponderance of {111} surface planes and suggests a strategy to enhance the area of desired surfaces in nanoparticles for better catalyst support activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Influence of Dopant Distribution on the Plasmonic Properties of Indium Tin Oxide Nanocrystals

Doped metal oxide nanocrystals represent an exciting frontier for colloidal synthesis of plasmonic materials, displaying unique optoelectronic properties and showing promise for a variety of applications. However, fundamental questions about the nature of doping in these materials remain. In this article, the strong influence of radial dopant distribution on the optoelectronic properties of colloidal indium tin oxide nanocrystals is reported. Comparing elemental depth-profiling by X-ray photoelectron spectroscopy (XPS) with detailed modeling and simulation of the optical extinction of these nanocrystals using the Drude model for free electrons, a correlation between surface segregation of tin ions and the average activation of dopants is observed. A strong influence of surface segregation of tin on the line shape of the localized surface plasmon resonance (LSPR) is also reported. Samples with tin segregated near the surface show a symmetric line shape that suggests weak or no damping of the plasmon by ionized impurities. It is suggested that segregation of tin near the surface facilitates compensation of the dopant ions by electronic defects and oxygen interstitials, thus reducing activation. A core shell model is proposed to explain the observed differences in line shape. These results demonstrate the nuanced role of dopant distribution in determining the optoelectronic properties of semiconductor nanocrystals and suggest that more detailed study of the distribution and structure of defects in plasmonic colloidal nanocrystals is warranted.

Lounis, SD↗
DOE OSTI2015

Atomic Structure of Pt 3 Ni Nanoframe Electrocatalysts by in Situ X-ray Absorption Spectroscopy

Understanding the atomic structure of a catalyst is crucial to exposing the source of its performance characteristics. It is highly unlikely that a catalyst remains the same under reaction conditions when compared to as-synthesized. Hence, the ideal experiment to study the catalyst structure should be performed in situ. Here, we use X-ray absorption spectroscopy (XAS) as an in situ technique to study Pt3Ni nanoframe particles which have been proven to be an excellent electro catalyst for the oxygen reduction reaction (ORR). The surface characteristics of the nanoframes were probed through electrochemical hydrogen underpotential deposition and carbon monoxide electrooxidation, which showed that nanoframe surfaces with different structure exhibit varying levels of binding strength to adsorbate molecules. It is well-known that Pt-skin formation on Pt-Ni catalysts will enhance ORR activity by weakening the binding energy between the surface and adsorbates. Ex situ and in situ XAS results reveal that nanoframes which bind adsorbates more strongly have a rougher Pt surface caused by insufficient segregation of Pt to the surface and consequent Ni dissolution. In contrast, nanoframes which exhibit extremely high ORR activity simultaneously demonstrate more significant segregation of Pt over Ni-rich subsurface layers, allowing better formation of the critical Pt-skin. This work demonstrates that the high ORR activity of the Pt3Ni hollow nanoframes depends on successful formation of the Pt-skin surface structure.

Becknell, Nigel↗
DOE OSTI2018

Isotopic analysis of deuterated water via single- and double-pulse laser-induced breakdown spectroscopy

Spatial segregation of species presents one of the main challenges in quantitative spectroscopy of laser-produced plasmas, as it may lead to overestimation of the concentration of the heavier species. Analytical capabilities can also be affected by excessive Stark broadening at atmospheric pressure, hindering the ability to spectrally resolve closely spaced spectral lines, such as those belonging to isotopes of the same element. We present an experimental and modeling study of the segregation of species and spectral line broadening in D 2 O-H 2 O plasma produced by single- and double-pulse nanosecond laser ablation in air. The ability to resolve Balmer spectral lines of hydrogen and deuterium is investigated by considering the effects of plume segregation. Transient plasma properties which lead to improvements in spectral line separation are discussed. While the plume segregation is found to be negligible in air regardless of the ablation scheme used, we observe a significant improvement in the separation of isotopic spectral lines by employing the double-pulse excitation. This study may lead to increased reliability of optical emission spectroscopy in deuterium-rich plasma environments and suggests the potential for sensitive detection of tritium in air via laser-induced breakdown spectroscopy

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Phase-field modeling of radiation-induced composition redistribution: An application to additively manufactured austenitic Fe–Cr–Ni

Multicomponent alloys undergoing irradiation damage develop radiation-induced composition redistribution at point defect sinks such as grain boundaries (GBs) and dislocations. Such redistribution results in undesired changes to their mechanical behavior and corrosion resistance. Additively manufactured alloys proposed for future nuclear applications are expected to demonstrate a distinct response to irradiation owing to their unique microstructure with as-solidified dislocation density and chemical microsegregation. To capture the composition redistribution in such systems, we develop a mesoscale model with coupled evolution of atomic and point defect components in the presence of dislocation density, dislocation heterogeneity, and thermodynamic interactions at the GB. The model is parameterized for an FCC Fe–Cr–Ni alloy as a representative system for austenitic stainless steels, and simulations are performed in 1D and 2D as a function of irradiation temperature, dose, dislocation density, and grain size. Radiation-induced segregation (RIS) characterized by Cr depletion and Ni enrichment is predicted at both the GB and the dislocation cell wall, with RIS being lower in magnitude but wider at the cell wall. Strongly biased absorption of self-interstitials by dislocations is found to suppress Ni enrichment but slightly enhance Cr depletion under certain conditions. Thermodynamic segregation at the GB is predicted to be narrower and opposite in sign to RIS for both Cr and Ni. Importantly, non-monotonic segregation is found to occur when both thermodynamic and RIS mechanisms are considered, providing a novel physical interpretation of experimental observations. The model is expected to serve as a key tool in accelerated qualification of irradiated materials.

additively manufactured microstructure↗
DOE OSTI2022

Unraveling Thermodynamic and Kinetic Contributions to the Stability of Doped Nanocrystalline Alloys using Nanometallic Multilayers

Abstract Targeted doping of grain boundaries is widely pursued as a pathway for combating thermal instabilities in nanocrystalline metals. However, certain dopants predicted to produce grain‐boundary‐segregated nanocrystalline configurations instead form small nanoprecipitates at elevated temperatures that act to kinetically inhibit grain growth. Here, thermodynamic modeling is implemented to select the Mo–Au system for exploring the interplay between thermodynamic and kinetic contributions to nanostructure stability. Using nanoscale multilayers and in situ transmission electron microscopy thermal aging, evolving segregation states and the corresponding phase transitions are mapped with temperature. The microstructure is shown to evolve through a transformation at lower homologous temperatures (<600 °C) where solute atoms cluster and segregate to the grain boundaries, consistent with predictions from thermodynamic models. An increase in temperature to 800 °C is accompanied by coarsening of the grain structure via grain boundary migration but with multiple pinning events uncovered between migrating segments of the grain boundary and local solute clustering. Direct comparison between the thermodynamic predictions and experimental observations of microstructure evolution thus demonstrates a transition from thermodynamically preferred to kinetically inhibited nanocrystalline stability and provides a general framework for decoupling contributions to complex stability transitions while simultaneously targeting a dominant thermal stability regime.

25 ENERGY STORAGE↗