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At least 775 records · Page 43
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Synthesis and spectral study of new azo dye and its iron complexes derived from 2-naphthol and 2-amino-3-hydroxypyridine

An azodye C{sub 5}H{sub 12}N{sub 3}O{sub 2} [LH] is synthesised by coupling diazotised 2-amino-3-hydroxy pyridine with 2-naphthol in ice cold condition. The Fe(II)and Fe(III) complexes were prepared by mixing ethanol solution of metal salt and azodye in 1:2 molar ratio. The dye and metal complexes are structurally characterised by elemental analysis, molar conductance, magnetic susceptibility measurements and spectral techniques like IR, UV-Vis, and Mössbauer analysis. Analytical data suggests the stoichiometry as [FeL{sub 2}Cl(H{sub 2}O)] for Fe(III) complex and [FeL{sub 2}(H{sub 2}O)] for Fe(II) complex. The IR spectral data suggests that [L{sup −}] is acting as a uninegative bidentate ligand. A high spin octahedral geometry is tentatively proposed for both the complexes with respect to the above studies.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Surface reconstructions in molecular beam epitaxy of SrTiO{sub 3}

We show that reflection high-energy electron diffraction (RHEED) can be used as a highly sensitive tool to track surface and resulting film stoichiometry in adsorption-limited molecular beam epitaxy of (001) SrTiO{sub 3} thin films. Even under growth conditions that yield films with a lattice parameter that is identical to that of stoichiometric bulk crystals within the detection limit of high-resolution x-ray diffraction (XRD), changes in surface reconstruction occur from (1 × 1) to (2 × 1) to c(4 × 4) as the equivalent beam pressure of the Ti metalorganic source is increased. These surface reconstructions are correlated with a shift from mixed SrO/TiO{sub 2} termination to pure TiO{sub 2} termination. The crossover to TiO{sub 2} surface termination is also apparent in a phase shift in RHEED oscillations observed at the beginning of growth. Comparison with prior results for carrier mobilities of doped films shows that the best films are grown under conditions of a TiO{sub 2}-saturated surface [c(4 × 4) reconstruction] within the XRD growth window.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Novel phases of lithium-aluminum binaries from first-principles structural search

Intermetallic Li–Al compounds are on the one hand key materials for light-weight engineering, and on the other hand, they have been proposed for high-capacity electrodes for Li batteries. We determine from first-principles the phase diagram of Li–Al binary crystals using the minima hopping structural prediction method. Beside reproducing the experimentally reported phases (LiAl, Li{sub 3}Al{sub 2}, Li{sub 9}Al{sub 4}, LiAl{sub 3}, and Li{sub 2}Al), we unveil a structural variety larger than expected by discovering six unreported binary phases likely to be thermodynamically stable. Finally, we discuss the behavior of the elastic constants and of the electric potential profile of all Li–Al stable compounds as a function of their stoichiometry.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Electrophilic surface sites as precondition for the chemisorption of pyrrole on GaAs(001) surfaces

We report how the presence of electrophilic surface sites influences the adsorption mechanism of pyrrole on GaAs(001) surfaces. For this purpose, we have investigated the adsorption behavior of pyrrole on different GaAs(001) reconstructions with different stoichiometries and thus different surface chemistries. The interfaces were characterized by x-ray photoelectron spectroscopy, scanning tunneling microscopy, and by reflectance anisotropy spectroscopy in a spectral range between 1.5 and 5 eV. On the As-rich c(4 × 4) reconstruction that exhibits only nucleophilic surface sites, pyrrole was found to physisorb on the surface without any significant modification of the structural and electronic properties of the surface. On the Ga-rich GaAs(001)-(4 × 2)/(6 × 6) reconstructions which exhibit nucleophilic as well as electrophilic surface sites, pyrrole was found to form stable covalent bonds mainly to the electrophilic (charge deficient) Ga atoms of the surface. These results clearly demonstrate that the existence of electrophilic surface sites is a crucial precondition for the chemisorption of pyrrole on GaAs(001) surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Record Seebeck coefficient and extremely low thermal conductivity in nanostructured SnSe

SnSe has been prepared by arc-melting, as mechanically robust pellets, consisting of highly oriented polycrystals. This material has been characterized by neutron powder diffraction (NPD), scanning electron microscopy, and transport measurements. A microscopic analysis from NPD data demonstrates a quite perfect stoichiometry SnSe{sub 0.98(2)} and a fair amount of anharmonicity of the chemical bonds. The Seebeck coefficient reaches a record maximum value of 668 μV K{sup −1} at 380 K; simultaneously, this highly oriented sample exhibits an extremely low thermal conductivity lower than 0.1 W m{sup −1} K{sup −1} around room temperature, which are two of the main ingredients of good thermoelectric materials. These excellent features exceed the reported values for this semiconducting compound in single crystalline form in the moderate-temperatures region and highlight its possibilities as a potential thermoelectric material.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Spin-modified catalysis

First-principle calculations are used to explore the use of magnetic degrees of freedom in catalysis. We use the Vienna Ab-Initio Simulation Package to investigate both L1{sub 0}-ordered FePt and CoPt bulk materials and perform supercell calculations for FePt nanoclusters containing 43 atoms. As the catalytic activity of transition-metal elements and alloys involves individual d levels, magnetic alloying strongly affects the catalytic performance, because it leads to shifts in the local densities of states and to additional peaks due to magnetic-moment formation. The peak shift persists in nanoparticles but is surface-site specific and therefore depends on cluster size. Our research indicates that small modifications in stoichiometry and cluster size are a useful tool in the search for new catalysts.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Structural and optical investigations of oxygen defects in zinc oxide nanoparticles

ZnO nanoparticles (NPs) were prepared implementing chemical precipitation method. Structural and optical characterizations of synthesized ZnO NPs were thoroughly probed applying X-ray diffraction (XRD), transmission electron microscope (TEM), energy dispersive X-ray (EDX) analysis, X-ray photoelectron spectroscopy (XPS), UV- Visible absorption and fluorescence (FL) spectroscopy. The XRD and TEM analyses revealed hexagonal wurtzite phase with 25-30 nm size. EDX analysis indicated oxygen (O) rich composition of nanoparticles. In accordance with EDX, XPS analysis verifies O{sub i} rich stoichiometry of prepared NPs. Furthermore, concurrence of lattice oxygen (O{sub L}), interstitial oxygen (O{sub i}) and oxygen vacancy (V{sub O}) in ZnO NPs was demonstrated through XPS analysis. Size quantization of nanoparticles is evident by blue shift of UV-Visible absorption energy. The FL spectroscopic investigations ascertain the existence of several discrete and defect states and radiative transitions occurring therein. Display of visible emission from oxygen defect states and most importantly, excess of O{sub i} defects in prepared ZnO nanoparticles, was well established through FL study.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Effect of doping of tin on optoelectronic properties of indium oxide: DFT study

Indium tin oxide is widely used transparent conductor. Experimentally observed that 6% tin doping in indium oxide is suitable for optoelectronic applications and more doping beyond this limit degrades the optoelectronic property. The stoichiometry (In{sub 32-x}Sn{sub x}O{sub 48+x/2}; x=0-6) is taken to understand the change in lattice parameter, electronic structure, and optical property of ITO. It is observed that lattice parameter increases and becomes constant after 6% tin doping that is in good agreement of the experimental observation. The electronic structure calculation shows that the high tin doping in indium oxide adversely affects the dispersive nature of the bottom of conduction band of pure indium oxide and decreases the carrier mobility. Optical calculations show that transmittance goes down upto 60% for the tin concentration more than 6%. The present paper shows that how more than 6% tin doping in indium oxide adversely affects the optoelectronic property of ITO.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Oxygen vacancy induced magnetization switching in Fe{sub 3}O{sub 4} epitaxial ultrathin films on GaAs(100)

The magnetic and transport properties of half metallic Fe{sub 3}O{sub 4}, which are sensitive to the stoichiometry, are the key issue for applications in spintronics. An anomalous enlargement of the saturation magnetic moment is found in a relatively thick sample of epitaxial Fe{sub 3}O{sub 4} film by post-growth oxidation method. The investigation of the thickness dependence of magnetic moment suggests that the enhanced magnetism moment may come from the existence of oxygen vacancies. First-principles calculations reveal that with oxygen vacancies in Fe{sub 3}O{sub 4} crystal the spin of Fe ions in the tetrahedron site near the vacancy is much easier to switch parallel to the Fe ions in the octahedron site by temperature disturbance, supported by the temperature dependence of magnetic moment of Fe{sub 3}O{sub 4} films in experiment.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Electronic and magnetic properties of off-stoichiometric Co{sub 2}Mn{sub β}Si/MgO interfaces studied by x-ray magnetic circular dichroism

We have studied the electronic and magnetic states of Co and Mn atoms at the interface of the Co{sub 2}Mn{sub β}Si (CMS)/MgO (β = 0.69, 0.99, 1.15, and 1.29) magnetic tunnel junction (MTJ) by means of x-ray magnetic circular dichroism. In particular, the Mn composition (β) dependences of the Mn and Co magnetic moments were investigated. The experimental spin magnetic moments of Mn, m{sub spin}(Mn), derived from x-ray magnetic circular dichroism weakly decreased with increasing Mn composition β in going from Mn-deficient to Mn-rich CMS films. This behavior was explained by first-principles calculations based on the antisite-based site-specific formula unit (SSFU) composition model, which assumes the formation of only antisite defect, not vacancies, to accommodate off-stoichiometry. Furthermore, the experimental spin magnetic moments of Co, m{sub spin}(Co), also weakly decreased with increasing Mn composition. This behavior was consistently explained by the antisite-based SSFU model, in particular, by the decrease in the concentration of Co{sub Mn} antisites detrimental to the half-metallicity of CMS with increasing β. This finding is consistent with the higher tunnel magnetoresistance ratios which have been observed for CMS/MgO/CMS MTJs with Mn-rich CMS electrodes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Carbon-rich hexagonal (BN)C alloys

Thin films of hexagonal boron nitride carbon, h-(BN){sub 1−x}(C{sub 2}){sub x}, alloys in the C-rich side have been synthesized by metal-organic chemical vapor deposition (MOCVD) on c-plane sapphire substrates. X-ray diffraction measurements confirmed single hexagonal phase of h-(BN){sub 1−x}(C{sub 2}){sub x} epilayers. Electrical transport and Raman spectroscopy measurements results revealed evidences that homogenous h-(BN){sub 1−x}(C{sub 2}){sub x} alloys with x ≥ 95% can be synthesized by MOCVD at a growth temperature of 1300 °C. The variable temperature Hall-effect measurements suggested that a bandgap opening of about 93 meV with respect to graphite has been obtained for h-(BN){sub 1−x}(C{sub 2}){sub x} with x = 0.95, which is consistent with the expected value deduced from the alloy dependence of the energy gap of homogenous h-(BN){sub 1−x}(C{sub 2}){sub x} alloys. Atomic composition results obtained from x-ray photoelectron spectroscopy measurements revealed that the carrier type in C-rich h-(BN){sub 1−x}(C{sub 2}){sub x} alloys is controlled by the stoichiometry ratio between the B and N via changing the V/III ratio during the growth. The demonstration of bandgap opening and conductivity control in C-rich h-(BN){sub 1−x}(C{sub 2}){sub x} alloys provide feasibilities for realizing technologically significant devices including infrared (IR) emitters and detectors active from near to far IR and multi-spectral IR emitters and detectors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Self-regulated growth of LaVO{sub 3} thin films by hybrid molecular beam epitaxy

LaVO{sub 3} thin films were grown on SrTiO{sub 3} (001) by hybrid molecular beam epitaxy. A volatile metalorganic precursor, vanadium oxytriisopropoxide (VTIP), and elemental La were co-supplied in the presence of a molecular oxygen flux. By keeping the La flux fixed and varying the VTIP flux, stoichiometric LaVO{sub 3} films were obtained for a range of cation flux ratios, indicating the presence of a self-regulated growth window. Films grown under stoichiometric conditions were found to have the largest lattice parameter, which decreased monotonically with increasing amounts of excess La or V. Energy dispersive X-ray spectroscopy and Rutherford backscattering measurements were carried out to confirm film compositions. Stoichiometric growth of complex vanadate thin films independent of cation flux ratios expands upon the previously reported self-regulated growth of perovskite titanates using hybrid molecular beam epitaxy, thus demonstrating the general applicability of this growth approach to other complex oxide materials, where a precise control over film stoichiometry is demanded by the application.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Origin of green luminescence in hydrothermally grown ZnO single crystals

Combining photoluminescence and positron annihilation studies of hydrothermally grown ZnO crystals with stoichiometry varied by controlled annealing enabled us to clarify the origin of green luminescence. It was found that green luminescence in ZnO has multiple origins and consists of a band at 2.3(1) eV due to recombination of electrons of the conduction band by zinc vacancy acceptors coupled with hydrogen and a band at 2.47(2) eV related to oxygen vacancies. The as-grown ZnO crystals contain zinc vacancies associated with hydrogen and exhibit a green luminescence at 2.3(1) eV. Annealing in Zn vapor removed zinc vacancies and introduced oxygen vacancies. This led to disappearance of the green luminescence band at 2.3(1) eV and appearance of a green emission at higher energy of 2.47(2) eV. Moreover, the color of the crystal was changed from colorless to dark red. In contrast, annealing of the as-grown crystal in Cd vapor did not remove zinc vacancies and did not cause any significant change of green luminescence nor change in coloration.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Growing LaAlO{sub 3}/SrTiO{sub 3} interfaces by sputter deposition

Sputter deposition of oxide materials in a high-pressure oxygen atmosphere is a well-known technique to produce thin films of perovskite oxides in particular. Also interfaces can be fabricated, which we demonstrated recently by growing LaAlO{sub 3} on SrTiO{sub 3} substrates and showing that the interface showed the same high degree of epitaxy and atomic order as is made by pulsed laser deposition. However, the high pressure sputtering of oxides is not trivial and number of parameters are needed to be optimized for epitaxial growth. Here we elaborate on the earlier work to show that only a relatively small parameter window exists with respect to oxygen pressure, growth temperature, radiofrequency power supply and target to substrate distance. In particular the sensitivity to oxygen pressure makes it more difficult to vary the oxygen stoichiometry at the interface, yielding it insulating rather than conducting.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Field evaporation of ZnO: A first-principles study

With recent advances in atom probe tomography of insulators and semiconductors, there is a need to understand high electrostatic field effects in these materials as well as the details of field evaporation. We use density functional theory to study field effects in ZnO clusters calculating the potential energy curves, the local field distribution, the polarizability, and the dielectric constant as a function of field strength. We confirm that, as in MgO, the HOMO-LUMO gap of a ZnO cluster closes at the evaporation field strength signaling field-induced metallization of the insulator. Following the structural changes in the cluster at the evaporation field strength, we can identify the field evaporated species, in particular, we show that the most abundant ion, Zn{sup 2+}, is NOT post-ionized but leaves the surface as 2+ largely confirming the experimental observations. Our results also help to explain problems related to stoichiometry in the mass spectra measured in atom probe tomography.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

A new form of Ca{sub 3}P{sub 2} with a ring of Dirac nodes

We report the synthesis and crystal structure of a new high-temperature form of Ca{sub 3}P{sub 2}. The crystal structure was determined through Rietveld refinements of synchrotron powder x-ray diffraction data. This form of Ca{sub 3}P{sub 2} has a crystal structure of the hexagonal Mn{sub 5}Si{sub 3} type, with a Ca ion deficiency compared to the ideal 5:3 stoichiometry. This yields a stable, charge-balanced compound of Ca{sup 2+} and P{sup 3−}. We also report the observation of a secondary hydride phase, Ca{sub 5}P{sub 3}H, which again is a charge-balanced compound. The calculated band structure of Ca{sub 3}P{sub 2} indicates that it is a three-dimensional Dirac semimetal with a highly unusual ring of Dirac nodes at the Fermi level. The Dirac states are protected against gap opening by a mirror plane in a manner analogous to what is seen for graphene.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Micro-structural characterization of low resistive metallic Ni germanide growth on annealing of Ni-Ge multilayer

Nickel-Germanides are an important class of metal semiconductor alloys because of their suitability in microelectronics applications. Here we report successful formation and detailed characterization of NiGe metallic alloy phase at the interfaces of a Ni-Ge multilayer on controlled annealing at relatively low temperature ∼ 250 °C. Using x-ray and polarized neutron reflectometry, we could estimate the width of the interfacial alloys formed with nanometer resolution and found the alloy stoichiometry to be equiatomic NiGe, a desirable low-resistance interconnect. We found significant drop in resistance (∼ 50%) on annealing the Ni-Ge multilayer suggesting metallic nature of alloy phase at the interfaces. Further we estimated the resistivity of the alloy phase to be ∼ 59μΩ cm.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Tuning thermal conductivity in homoepitaxial SrTiO{sub 3} films via defects

We demonstrate the ability to tune the thermal conductivity of homoepitaxial SrTiO{sub 3} films deposited by reactive molecular-beam epitaxy by varying growth temperature, oxidation environment, and cation stoichiometry. Both point defects and planar defects decrease the longitudinal thermal conductivity (k{sub 33}), with the greatest decrease in films of the same composition observed for films containing planar defects oriented perpendicular to the direction of heat flow. The longitudinal thermal conductivity can be modified by as much as 80%—from 11.5 W m{sup −1}K{sup −1} for stoichiometric homoepitaxial SrTiO{sub 3} to 2 W m{sup −1}K{sup −1} for strontium-rich homoepitaxial Sr{sub 1+δ}TiO{sub x} films—by incorporating (SrO){sub 2} Ruddlesden-Popper planar defects.

36 MATERIALS SCIENCE↗