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At least 1,585 records · Page 88
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Effects of rare earth substitution on the optical properties of Bi{sub 2}MoO{sub 6} for coloring applications

Highlights: • New class of colored compounds BiREMoO{sub 6} (RE = Pr, Nd, Sm, Tb, Yb) was synthesized. • The substitution of RE gently red shifts the absorption edge to low energy side. • The differences in band gap depend on the position of the RE f bands. • The yellow colored compounds demonstrated good coloration to plastics. - Abstract: A new class of colored inorganic compounds, BiREMoO{sub 6} (RE = Pr, Nd, Sm, Tb and Yb) has been synthesized by a solid state route. The substitution of different rare earths for Bi{sup 3+} in Bi{sub 2}MoO{sub 6} produces visible light responsive compounds by gently red shifting the absorption edge to low energy side. The visible light absorption is based on the charge transfer transitions from O{sub 2p} valence band to conduction band made of primary Mo{sub 4d} and secondary Bi{sub 6p}. The substitution of RE{sup 3+} introduces partially occupied 4f electronic levels in between the band gap and the position of 4f level depend on the number of f electrons which allows tuning the band gap. Thus the rare earth substitution provides an opportunity to tailor the band gap of Bi{sub 2}MoO{sub 6} from 2.99 eV to 2.19 eV. The developed compounds exhibited different shades of yellow hue and demonstrated good coloration to plastics.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Rondorfite-type structure — XPS and UV–vis study

Highlights: • Structural and spectroscopic characterization of chlorosilicate mineral, rondorfite. • Characterization of main photoemission lines and valence band spectra. • The study of color origin’s using UV–vis spectroscopy. • Analysis of structural changes in context of origin of natural fluorescence. • Discussion of a new application possibilities of analyzed mineral - Abstract: This paper focuses on X-ray diffraction, X-ray photoelectron and UV–vis spectroscopy of two different (green, orange) rondorfite samples. The differences in the sample color originate from various O/Cl ratios. The orange color was found to be related either to the isomorphic substitution of Fe{sup 3+}/Al{sup 3+} for Mg{sup 2+}, the presence of atypical [MgO{sub 4}] tetrahedrons in crystal structure or electronegativity of the sample. The tetrahedron is known to be very prone to accumulation of impurities and substitute atoms. Moreover, the XPS data showed tetrahedrally coordinated Mg{sup 2+} and isomorphic substitution of Al{sup 3+}/Fe{sup 3+} for Mg{sup 2+}, which influences local disordering and the point defects density and distribution. Non-equilibrium chlorine positions inside the crystal cages as well as Ca-Cl bonds have also been found. The XPS measurements as a function of temperature indicate occurrence of a structural transformation at about 770 K which is accompanied by a rotation of silicate tetrahedra within magnesiosilicate pentamer and luminescence disappearance.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Structural, magnetic, and Mössbauer spectroscopy of Cu substituted M-type hexaferrites

Highlights: • Single BaM hexaferrite structural phases with Cu substations were prepared. • The magnetocrystalline anisotropy decreased with Cu substitution. • The coercivity was significantly modified while the magnetization remained high. • Hexaferrites with 0.2–0.4 Cu possess properties suitable for magnetic recording. • Ionic distributions from structural refinement agreed with Mössbauer spectroscopy. - Abstract: BaFe{sub 12−x}Cu{sub x}O{sub 19} hexaferrites were prepared using ball milling and sintering at 1100 °C. Refinement of the X-ray diffraction patterns was carried out to determine the structural parameters and the ionic distribution over the crystallographic sites. The preferential site occupation and valence state of Cu was consistent with the results obtained from the analysis of Mössbauer spectra. Further, the magnetic parameters of the samples were discussed in light of the structural and Mössbauer analyses. The magnetic phase transition temperature was found to decrease with the level of Cu substitution, in accordance with the reduction of the superexchange interactions. Further, the magnetic softening of the hexaferrite and the significant reduction in magnetocrystalline anisotropy with Cu substitution was consistent with the ionic distribution in the lattice. This study clearly demonstrated the feasibility of using a simple method to fabricate hexaferrites with a modified coercivity, while maintain the saturation magnetization high enough for practical applications.

36 MATERIALS SCIENCE↗
DOE OSTI2016

In-situ plasma hydrogenated TiO{sub 2} thin films for enhanced photoelectrochemical properties

Highlights: • Growth of TiO{sub 2} thin films with in-situ plasma hydrogenation. • Presence of Ti{sup 2+} states in addition to Ti{sup 3+} states present in pristine TiO{sub 2}. • Change in VBM, work function and band gap in iH:TiO{sub 2}. • Enhanced photocurrent density as compared to pristine TiO{sub 2} films. - Abstract: In this paper, we report the effect of in-situ plasma hydrogenation of TiO{sub 2} (iH:TiO{sub 2}) thin films by the incorporation of known amount of hydrogen in the Ar plasma during rf-sputter deposition of TiO{sub 2} films. As compared to pristine TiO{sub 2} films (∼0.43 mA/cm2 at 0.23 V vs Ag/AgCl), hydrogenated TiO{sub 2} showed enhanced photoelectrochemical activity in terms of improved photocurrent density of ∼1.08 mA/cm2 (at 0.23 V vs Ag/AgCl). These results are explained in terms of reduction in band gap energy, shift in valence band maximum away from the Fermi level, improved donor density and more negative flat band potential in iH:TiO{sub 2} sample. The presence of Ti{sup 2+} states in iH:TiO{sub 2} films in addition to Ti{sup 3+} states in pristine TiO{sub 2} act as additional electronic states in the TiO{sub 2} band gap and increases the optical absorption in the visible region. This method of in-situ hydrogenation can be used as a general method for improving the properties of metal oxide thin films for photoelectrochemical and photocatalytic applications.

36 MATERIALS SCIENCE↗
DOE OSTI2016

X-ray photoemission spectroscopy investigation of CaTiO{sub 3}:Eu for luminescence property: effect of Eu{sup 3+} ion

Graphical abstract: The influence on the photoluminescent performance due to the electronic structure change in Eu-doped CaTiO{sub 3} of the specific core-level and valence band spectrum via X-ray photoemission spectroscopy were characterized. - Highlights: • Single phase CaTiO{sub 3} and CaTiO{sub 3}: Eu crystals were prepared under mild hydrothermal method. • Crystal structure, doping level and the relations to their luminescent property were discussed. • Charge compensation mechanism was discussed via valance band spectrum by XPS. - Abstract: Charge compensation of on-site Eu 4f–5d transition that determines the luminescent performance was confirmed with valance band spectrum. Influence of photoelectrons from CaTiO{sub 3}: Eu to the corresponding luminescent performance was discussed based on the crystal structure, doping level and the relations to their luminescent property. This paper is important to further optimize the luminescent performance for improving the efficiency and reducing the cost in light emitting diode industry.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Structural and magnetic properties of La2Ni1−xCoxMnO6 compounds

Highlights: • Monoclinic La2Ni1−xCoxMnO6 samples have been prepared using Sol-gel technique. • Rietveld analysis shows an octahedrally distorted double perovskite structure. • The nature of FM interaction and TC depend on the B-site ions. • The short range FM ordering above TC is induced by antisite disorders. • The existence of any spin glass like phase in such system is discarded. - Abstract: Single phase monoclinic La{sub 2}Ni{sub 1−x}Co{sub x}MnO{sub 6} (x = 0.2, 0.4, 0.8) compounds, henceforth, referred as LNC{sub x}MO (x = 0.2, 0.4, 0.8) have been prepared by Sol–gel technique. The structural study and redox titration suggest that the samples are both La and O deficient. The generated atomic models using Rietveld refined structural parameters show octahedral distortion in the double perovskite structure. X-ray photoelectron spectroscopy (XPS) study has been used to determine the predominant valence states of Ni, Mn and Co ions. LNC{sub x}MO (x = 0.2, 0.4) are found to be Heisenberg ferromagnets whereas LNC{sub 0.8}MO is a phase segregated system. In LNC{sub 0.4}MO and LNC{sub 0.8}MO, at temperatures above T{sub C}, χ{sup −1}(T) curve shows the characteristics of Griffiths phase. The study of ac susceptibility and isothermal remanent magnetization (IRM) discard the possibility of any glassy state at low temperatures. The antiphase boundaries (APBs), antisite disorders (ASDs) and oxygen vacancies play important roles in this system.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Te-doped perovskite NaTaO3 as a promising photocatalytic material for hydrogen production from water splitting driven by visible light

Highlights: • S, Se and Te-doped NaTaO{sub 3} is a promising material for photocatalytic water splitting. • Enhanced absorption coefficient in the visible light range is identified for Te-doped NaTaO{sub 3}. • Te-doped NaTaO{sub 3} exhibits higher electron and hole mobility than pristine NaTaO{sub 3}. - Abstract: The photocatalytic hydrogen production from water splitting can be achieved by using the pristine NaTaO{sub 3} experimentally, but the reaction cannot be driven by the visible light because of the wide band gap of NaTaO{sub 3}. The present work focuses on tuning the photocatalytic performance of NaTaO{sub 3} into the visible light range by doping S, Se, and Te elements. The obvious decrease in band energy gaps (E{sub g}s) and noticeable red-shift of the absorption edges are observed for the doped structures. The valence band maximum and conduction band minimum of the doped structures satisfy the requirement of the water splitting. Moreover, a significant enhancement of absorption coefficient in the visible light range is observed for the doped structure of Te@O. The calculated carrier mobility is used to evaluate the charge spatial separation of Te@O and the unusual increases and the obvious differences of the mobility of the electrons and holes are observed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Electronic structure and oxophilicity optimization of mono-layer Pt for efficient electrocatalysis

The slow kinetics of the anodic hydrogen oxidation reaction (HOR) in alkaline medium is one of the limitations for anion exchange membrane fuel cells (AEMFCs). Hence, accurately regulate and understand catalytic interface structure are essential to solve this bottleneck and reveal the structure-activity relationship. In this work, a novel trimetal core-shell model with mono-layer Pt-shell is employed for hydrogen electrooxidation to avoid thermodynamic driven bulk/surface composition deviation. On account of the atomic radius discrepancies of 3d-transition metals M (M = Fe, Co and Cu), the electronic structure of mono-layer Pt is regulated by the strain-engineered Pd-M core and the electrocatalytic activity for HOR is tuned accordingly. Nevertheless, step-by-step electrochemical monitoring and surface-treatment experiments indicate that the oxophilicity optimization by low-valence M(OH) x species, rather than the hydrogen binding energy (HBE) optimization caused by strain engineering, influence the activity obviously. It is mainly derived from the enhanced adsorption of OH ad and accelerated desorption of the H ad . The trimetal core-shell model breathes new life into the low-Pt catalyst design for hydrogen electrooxidation reaction.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Exchange of Ions across the TiN/TaO x Interface during Electroformation of TaO x -Based Resistive Switching Devices

The valence change model describes the resistive switching in metal oxide-based devices as due to electroreduction of the oxide and subsequent electromigration of oxygen vacancies. Here, we present cross-sectional X-ray energy-dispersive spectroscopy elemental maps of Ta, O, N, and Ti in electroformed TiN/TaO 2.0 /TiN structures. O, N, and Ti were exchanged between the anode and the functional oxide in devices formed at high power (~1 mW), but the exchange was below the detection limit at low power (<0.5 mW). All structures exhibit a similar Ta-enriched and O-depleted filament formed by the elemental segregation in the functional oxide by the temperature gradient. The elemental interchange is interpreted as due to Fick’s diffusion caused by high temperatures in the gap of the filament and is not an essential part of electroformation.

36 MATERIALS SCIENCE↗
DOE OSTI2013

The silicon/zinc oxide interface in amorphous silicon-based thin-film solar cells: Understanding an empirically optimized contact

The electronic structure of the interface between the boron-doped oxygenated amorphous silicon 'window layer' (a-SiO{sub x}:H(B)) and aluminum-doped zinc oxide (ZnO:Al) was investigated using hard x-ray photoelectron spectroscopy and compared to that of the boron-doped microcrystalline silicon ({mu}c-Si:H(B))/ZnO:Al interface. The corresponding valence band offsets have been determined to be (-2.87 {+-} 0.27) eV and (-3.37 {+-} 0.27) eV, respectively. A lower tunnel junction barrier height at the {mu}c-Si:H(B)/ZnO:Al interface compared to that at the a-SiO{sub x}:H(B)/ZnO:Al interface is found and linked to the higher device performances in cells where a {mu}c-Si:H(B) buffer between the a-Si:H p-i-n absorber stack and the ZnO:Al contact is employed.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Analysis of defects in GaAsN grown by chemical beam epitaxy on high index GaAs substrates

The lattice defects in GaAsN grown by chemical beam epitaxy on GaAs 311B and GaAs 10A toward [110] were characterized and discussed by using deep level transient spectroscopy (DLTS) and on the basis of temperature dependence of the junction capacitances (C{sub J}). In one hand, GaAsN films grown on GaAs 311B and GaAs 10A showed n-type and p-type conductivities, respectively although the similar and simultaneous growth conditions. This result is indeed in contrast to the common known effect of N concentration on the type of conductivity, since the surface 311B showed a significant improvement in the incorporation of N. Furthermore, the temperature dependence of C{sub J} has shown that GaAs 311B limits the formation of N-H defects. In the other hand, the energy states in the forbidden gap of GaAsN were obtained. Six electron traps, E1 to E6, were observed in the DLTS spectrum of GaAsN grown on GaAs 311B, with apparent activation energies of 0.02, 0.14, 0.16, 0.33, 0.48, and 0.74 eV below the bottom edge of the conduction band, respectively. In addition, four hole traps, H1 to H4, were observed in the DLTS spectrum of GaAsN grown on GaAs 10A, with energy depths of 0.13, 0.20, 0.39, and 0.52 eV above the valence band maximum of the alloy, respectively. Hence, the surface morphology of the GaAs substrate was found to play a key factor role in clarifying the electrical properties of GaAsN grown by CBE.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Growth and phase transition characteristics of pure M-phase VO{sub 2} epitaxial film prepared by oxide molecular beam epitaxy

VO{sub 2} epitaxial film with large size has been prepared by oxide-molecular beam epitaxy method on Al{sub 2}O{sub 3} (0001) substrate. The VO{sub 2} film shows a perfect crystal orientation, uniformity, and distinct metal-insulator phase transition (MIT) characteristics. It is observed that the MIT character is closely associated with the crystal defects such as oxygen vacancies. By controlling the growth condition, the MIT temperature can be tuned through modifying the content of oxygen vacancies. The role of the oxygen vacancies on the phase transition behavior of this VO{sub 2} film is discussed in the framework of the hybridization theory and the valence state of vanadium.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Demonstrating 1 nm-oxide-equivalent-thickness HfO{sub 2}/InSb structure with unpinning Fermi level and low gate leakage current density

In this work, the band alignment, interface, and electrical characteristics of HfO{sub 2}/InSb metal-oxide-semiconductor structure have been investigated. By using x-ray photoelectron spectroscopy analysis, the conduction band offset of 1.78 ± 0.1 eV and valence band offset of 3.35 ± 0.1 eV have been extracted. The transmission electron microscopy analysis has shown that HfO{sub 2} layer would be a good diffusion barrier for InSb. As a result, 1 nm equivalent-oxide-thickness in the 4 nm HfO{sub 2}/InSb structure has been demonstrated with unpinning Fermi level and low leakage current of 10{sup −4} A/cm{sup −2}. The D{sub it} value of smaller than 10{sup 12} eV{sup −1}cm{sup −2} has been obtained using conduction method.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Growth and properties of GaSbBi alloys

Molecular-beam epitaxy has been used to grow GaSb{sub 1−x}Bi{sub x} alloys with x up to 0.05. The Bi content, lattice expansion, and film thickness were determined by Rutherford backscattering and x-ray diffraction, which also indicate high crystallinity and that >98% of the Bi atoms are substitutional. The observed Bi-induced lattice dilation is consistent with density functional theory calculations. Optical absorption measurements and valence band anticrossing modeling indicate that the room temperature band gap varies from 720 meV for GaSb to 540 meV for GaSb{sub 0.95}Bi{sub 0.05}, corresponding to a reduction of 36 meV/%Bi or 210 meV per 0.01 Å change in lattice constant.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Enhanced hydrogenation and reduced lattice distortion in size selected Pd-Ag and Pd-Cu alloy nanoparticles

Important correlation between valence band spectra and hydrogenation properties in Pd alloy nanoparticles is established by studying the properties of size selected and monocrystalline Pd, Ag, Cu, Pd-Ag, and Pd-Cu nanoparticles. The X-ray photoelectron spectroscopy and elastic recoil detection analysis show that size induced Pd4d centroid shift is related to enhanced hydrogenation with H/Pd ratio of 0.57 and 0.49 in Pd-Ag and Pd-Cu nanoparticles in comparison to reported bulk values of 0.2 and 0.1, respectively. Pd-alloy nanoparticles show lower hydrogen induced lattice distortion. The reduced distortion and higher hydrogen reactivity of Pd-alloy nanoparticles is important for numerous hydrogen related applications.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Anomalous Hall effect in epitaxial permalloy thin films

Anomalous Hall effect (AHE) of epitaxial permalloy thin films grown on MgO (001) substrates is investigated. The longitudinal conductivity independent term (i.e., the sum of intrinsic and side-jump contributions) of the anomalous Hall conductivity (AHC) is found to be much smaller than those of Fe and Ni films. Band theoretical calculations of the intrinsic AHC as a function of the number of valence electrons (band filling) indicate that the AHC of the permalloy is in the vicinity of sign change, thus resulting in the smallness of the intrinsic AHC. The contribution of the phonon scattering is found to be comparable to that of the impurity scattering. This work suggests that the permalloy films are ideal systems to understand the AHE mechanisms induced by impurity scattering.

36 MATERIALS SCIENCE↗
DOE OSTI2013

An ab initio study on compressibility of Al-containing MAX-phase carbides

The compressibility of Al-containing MAX carbides was investigated in details using first-principle calculations based on density functional theory. The bond stiffness and bond angle as a function of pressure were examined. The M-Al bond stiffness is about 1/3–1/2 of M-C bond stiffness. The M-C bond close to Al atoms has the highest bond stiffness in M{sub 3}AlC{sub 2} and M{sub 4}AlC{sub 3} phases, with the similar bond stiffness of the other two bonds in the latter. Generally, the bond stiffness of the strongest M-C bond increases with increasing VEC (Valence Electron Concentration), which also affects the bond stiffness of other bonds. Of most importance, the bulk moduli are 0.256 of the mean bond stiffness for three series. With increasing pressure, M-Al bond angle increases, but M-C bond angles decreases, which indicates that M-Al and M-C bonds shift towards basal plane and along c-axis, respectively. As a result, the compressibility becomes more difficult along c-axis than a-axis. Some abnormal phenomena in the compressibility of Al-containing M{sub n+1}AlX{sub n} phases with VEC = 6 are attributed to the thermodynamical instability of these compounds.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Optical phonon modes in Al{sub 1−x}Sc{sub x}N

Optical phonons are measured to probe the origins of the reported anomalously high piezoelectric response in aluminum scandium nitride (Al{sub 1−x}Sc{sub x}N). Epitaxial layers with 0 ≤ x ≤ 0.16 deposited on sapphire(0001) exhibit a refractive index below the band gap, which increases from 2.03 for x = 0 to 2.16 for x = 0.16, corresponding to a dielectric constant ε{sub ∞} = 4.15 + 3.2x. Raman scattering shows that zone-center E{sub 2}(H) and A{sub 1}(TO) phonon modes shift to lower frequencies with increasing x, following linear relationships: ω(E{sub 2}(H)) = 658–233x (cm{sup −1}) and ω(A{sub 1}(TO)) = 612–159x (cm{sup −1}). Similarly, zone-center E{sub 1}(TO) and A{sub 1}(LO) phonon mode frequencies obtained from specular polarized infrared reflectance measurements red-shift to ω(E{sub 1}(TO)) = 681–209x (cm{sup −1}) and ω(A{sub 1}(LO)) = 868–306x (cm{sup −1}). The measured bond angle decreases linearly from 108.2° to 106.0°, while the length of the two metal-nitrogen bonds increase by 3.2% and 2.6%, as x increases from 0 to 0.16. This is associated with a 3%–8% increase in the Born effective charge and a simultaneous 6% decrease in the covalent metal-N bond strength, as determined from the measured vibrational frequencies described with a Valence-Coulomb-Force-Field model. The overall results indicate that bonding in Al-rich Al{sub 1−x}Sc{sub x}N qualitatively follows the trends expected from mixing wurtzite AlN with metastable hexagonal ScN. However, extrapolation suggests non-linear composition dependencies in bond angle, length, and character for x ≥ 0.2, leading to a structural instability that may be responsible for the reported steep increase in the piezoelectric response.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗