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At least 793 records · Page 44
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DOE OSTI2015

Controlling magnetic domain wall motion in the creep regime in He{sup +}-irradiated CoFeB/MgO films with perpendicular anisotropy

This study presents the effective tuning of perpendicular magnetic anisotropy in CoFeB/MgO thin films by He{sup +} ion irradiation and its effect on domain wall motion in a low field regime. Magnetic anisotropy and saturation magnetisation are found to decrease as a function of the irradiation dose which can be related to the observed irradiation-induced changes in stoichiometry at the CoFeB/MgO interface. These changes in the magnetic intrinsic properties of the film are reflected in the domain wall dynamics at low magnetic fields (H) where irradiation is found to induce a significant decrease in domain wall velocity (v). For all irradiation doses, domain wall velocities at low fields are well described by a creep law, where Ln(v) vs. H{sup −1∕4} behaves linearly, up to a maximum field H*, which has been considered as an approximation to the value of the depinning field H{sub dep}. In turn, H* ≈ H{sub dep} is seen to increase as a function of the irradiation dose, indicating an irradiation-induced extension of the creep regime of domain wall motion.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Characterization of the insulator barrier and the superconducting transition temperature in GdBa{sub 2}Cu{sub 3}O{sub 7−δ}/BaTiO{sub 3} bilayers for application in tunnel junctions

The optimization of the superconducting properties in a bottom electrode and the quality of an insulator barrier are the first steps in the development of superconductor/insulator/superconductor tunnel junctions. Here, we study the quality of a BaTiO{sub 3} tunnel barrier deposited on a 16 nm thick GdBa{sub 2}Cu{sub 3}O{sub 7−δ} thin film by using conductive atomic force microscopy. We find that the tunnel current is systematically reduced (for equal applied voltage) by increasing the BaTiO{sub 3} barrier thickness between 1.6 and 4 nm. The BaTiO{sub 3} layers present an energy barrier of ≈1.2 eV and an attenuation length of 0.35–0.5 nm (depending on the applied voltage). The GdBa{sub 2}Cu{sub 3}O{sub 7−δ} electrode is totally covered by a BaTiO{sub 3} thickness above 3 nm. The presence of ferroelectricity was verified by piezoresponse force microscopy for a 4 nm thick BaTiO{sub 3} top layer. The superconducting transition temperature of the bilayers is systematically suppressed by increasing the BaTiO{sub 3} thickness. This fact can be associated with stress at the interface and a reduction of the orthorhombicity of the GdBa{sub 2}Cu{sub 3}O{sub 7−δ}. The reduction in the orthorhombicity is expected by considering the interface mismatch and it can also be affected by reduced oxygen stoichiometry (poor oxygen diffusion across the BaTiO{sub 3} barrier)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

The mystery of missing species in atom probe tomography of composite materials

There is a serious problem in atom probe tomography of composite materials such as oxides that even from stoichiometric samples one observes non-stoichiometric ion yields. We present a quantitative model that explains the non-stoichiometry allowing a fit to experimental data of ion yields as a function of applied field to extract activation barriers and prefactors. The numbers are confirmed by density functional theory. We also show that for oxides the missing oxygen is thermally desorbed as neutral O{sub 2}, either directly or associatively. Finally, we suggest methods to improve the experimental setup.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Development of a dipodal Schiff base ligand with N-imine and O-naphtholate donors: A potential chelator towards Cu(II) metal ion established through potentiometric and spectrophotometric studies

A novel hydroxynaphthaldehyde derived Schiff base ligand N,N’-bis-[2-[(2-hydroxy-1-naphthyl)methyleneamino]ethyl]propanediamide (DOTA2HNAP) containing nitrogen and oxygen donor atoms has been developed. The lowest energy molecular structure of DOTA2HNAP and its complexes with Cu (II) metal ion were examined by molecular mechanics using MM+ force which later was re-optimized by semi-empirical method. The theoretical IR and UV spectra of the ligand were obtained using semi empirical/ZINDO/PM3 and were compared with the experimental ones. The coordinating ability of DOTA2HNAP with H{sup +} and Cu(II) ions was investigated in 1:99 (DMSO: water) binary solvent mixture at 25±1°C by potentiometric and spectrophotometric method. The electronic spectra of the ligand show three distinct peaks (253nm, 320nm and 360nm) implicating existence of the Schiff base in quinone form that was well supported by theoretical spectral studies. Out of various complex species forming in solution, all the metal ions show higher stability of complexes when in 1:1 metal-ligand stoichiometry, binding through two N-imine and two O-naphtholate groups.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Cu diffusion in single-crystal and polycrystalline TiN barrier layers: A high-resolution experimental study supported by first-principles calculations

Dense single-crystal and polycrystalline TiN/Cu stacks were prepared by unbalanced DC magnetron sputter deposition at a substrate temperature of 700 °C and a pulsed bias potential of −100 V. The microstructural variation was achieved by using two different substrate materials, MgO(001) and thermally oxidized Si(001), respectively. Subsequently, the stacks were subjected to isothermal annealing treatments at 900 °C for 1 h in high vacuum to induce the diffusion of Cu into the TiN. The performance of the TiN diffusion barrier layers was evaluated by cross-sectional transmission electron microscopy in combination with energy-dispersive X-ray spectrometry mapping and atom probe tomography. No Cu penetration was evident in the single-crystal stack up to annealing temperatures of 900 °C, due to the low density of line and planar defects in single-crystal TiN. However, at higher annealing temperatures when diffusion becomes more prominent, density-functional theory calculations predict a stoichiometry-dependent atomic diffusion mechanism of Cu in bulk TiN, with Cu diffusing on the N sublattice for the experimental N/Ti ratio. In comparison, localized diffusion of Cu along grain boundaries in the columnar polycrystalline TiN barriers was detected after the annealing treatment. The maximum observed diffusion length was approximately 30 nm, yielding a grain boundary diffusion coefficient of the order of 10{sup −16} cm{sup 2} s{sup −1} at 900 °C. This is 10 to 100 times less than for comparable underdense polycrystalline TiN coatings deposited without external substrate heating or bias potential. The combined numerical and experimental approach presented in this paper enables the contrasting juxtaposition of diffusion phenomena and mechanisms in two TiN coatings, which differ from each other only in the presence of grain boundaries.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Evolution of grain boundary conduction with increasing temperature in pure and Ti doped Co ferrite materials

We report on the structural, temperature, and frequency dependent impedance studies of Ti doped cobalt ferrite material (CoFe{sub 1.95}Ti{sub 0.05}O{sub 4}) in comparison with the pure CoFe{sub 2}O{sub 4}. XRD and Raman spectroscopy studies confirm the inverse spinel crystallization of the materials with space group of Fd-3 m. Scanning electron microscope images shows the microcrystalline nature of the particles. Homogeneity, stoichiometry, and ionic states of the ions in the composition were confirmed by energy dispersive X-ray analysis and X-ray photoelectron spectroscopic studies. Temperature and frequency dependent real (Z′) and imaginary (Z″) part of the impedance shows the existence of relaxation processes and their distribution in CoFe{sub 2}O{sub 4} and CoFe{sub 1.95}Ti{sub 0.05}O{sub 4} materials. Complex impedance spectroscopy studies at low temperatures shows that the conductivity in these materials is predominantly due to the intrinsic bulk grains. With increasing the temperature, evolution of grain boundary conduction is clearly seen through the appearance of a second semi-circle in the complex impedance plots. Room temperature total dc conductivity of both CoFe{sub 2}O{sub 4} and CoFe{sub 1.95}Ti{sub 0.05}O{sub 4} materials is found to be 5.78 × 10{sup −8} and 1.61 × 10{sup −7} S/cm, respectively. Temperature variation of dc electrical conductivity follows the Arrhenius relationship and the activation energies for CoFe{sub 2}O{sub 4} corresponding to grain (0.55 eV for CoFe{sub 2}O{sub 4}), grain boundary (0.52 eV), and total conduction (0.54 eV) are discussed. Observation of well distinguishable grain and grain boundary conductions and the low conductivity values in CoFe{sub 2}O{sub 4} and CoFe{sub 1.95}Ti{sub 0.05}O{sub 4} materials indicates that these materials are promising candidates for the high frequency applications.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Superconducting properties and chemical composition of NbTiN thin films with different thickness

In this research, we systematically investigated the superconducting properties and chemical composition of NbTiN thin films prepared on single-crystal MgO substrates. The NbTiN thin films with different thicknesses (4–100 nm) were deposited by reactive DC magnetron sputtering at ambient temperature. We measured and analyzed the crystal structure and thickness dependence of the chemical composition using X-ray diffraction and X-ray photoelectron spectroscopy depth profiles. The films exhibited excellent superconducting properties, with a high superconducting critical temperature of 10.1 K, low resistivity (ρ{sub 20} = 93 μΩ cm), and residual resistivity ratio of 1.12 achieved for 4-nm-thick ultrathin NbTiN films prepared at the deposition current of 2.4 A. The stoichiometry and electrical properties of the films varied gradually between the initial and upper layers. A minimum ρ{sub 20} of 78 μΩ cm and a maximum residual resistivity ratio of 1.15 were observed for 12-nm-thick films, which significantly differ from the properties of NbN films with the same NaCl structure.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Position-sensitive change in the transition metal L-edge fine structures

Studying the structure and composition of solid-state materials on the atomic scale has become nearly routine in transmission electron microscopy with the development of novel electron optics and electron sources. In particular, with spatial resolutions better than 0.1 nm and energy resolution smaller than 100 meV, the stoichiometry, bonding, and coordination can now be examined on similar scales. Aberration-corrected scanning transmission electron microscopy and electron energy-loss spectroscopy (EELS) have played a crucial role in identifying charge ordering, valence, and as spin state transitions in transition metal perovskite oxides. In this letter, we investigate the effects of ever-decreasing electron-probe sizes on the measured near-edge fine-structure of the transition metal core-loss edge using EELS. We find that for certain transition metal perovskites, the position of the electron probe with respect to the atomic column is crucial in determining the correct valence state. Several reasons for the observed position-sensitive EELS fine-structure are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Microstructure and defects probed by Raman spectroscopy in lithium niobate crystals and devices

Raman microprobe applied on LiNbO{sub 3} (LN) crystals and derived materials or devices is shown to be a tool to detect either local variations or changes of the whole structure. Position, width, or intensity of one Raman line can be used as markers of a structural change. Indeed, each Raman line can be assigned to a peculiar ionic motion and is differently sensitive to application of strain, temperature change, and electric field. Some vibrational modes are especially associated to the site of Li ion, or Nb ion, or still oxygen octahedron, so that they can be affected by the introduction of dopant ion on one or another site. Therefore, Raman Spectroscopy (RS) can be used as a site spectroscopy to describe the mechanism of doping incorporation in the LN lattice, allowing the optimization of some linear and non-linear optical properties according to the dopant concentration and substitution site. The composition or the content of non-stoichiometry related defects could be derived from the width of some lines. Any damage or local disorder can be detected by a line broadening. The quality or preservation of the structure after chemical treatment, or laser pulses, can be thus checked. The structure of ion-implanted or proton-exchanged wave-guides and periodically poled lithium niobate as well can be imaged from frequency shift or intensity change of some lines. RS is thus a useful way to control the structure of LN and/or to optimize the preparation parameters and its properties.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Electronic and optical properties of titanium nitride bulk and surfaces from first principles calculations

Prediction of the frequency-dependent dielectric function of thin films poses computational challenges, and at the same time experimental characterization by spectroscopic ellipsometry remains difficult to interpret because of changes in stoichiometry and surface morphology, temperature, thickness of the film, or substrate. In this work, we report calculations for titanium nitride (TiN), a promising material for plasmonic applications because of less loss and other practical advantages compared to noble metals. We investigated structural, electronic, and optical properties of stoichiometric bulk TiN, as well as of the TiN(100), TiN(110), and TiN(111) outermost surfaces. Density functional theory (DFT) and many-body GW methods (Green's (G) function-based approximation with screened Coulomb interaction (W)) were used, ranging from G{sub 0}W{sub 0}, GW{sub 0} to partially self-consistent sc-GW{sub 0}, as well as the GW-BSE (Bethe-Salpeter equation) and time-dependent DFT (TDDFT) methods for prediction of the optical properties. Structural parameters and the band structure for bulk TiN were shown to be consistent with previous work. Calculated dielectric functions, plasma frequencies, reflectivity, and the electron energy loss spectrum demonstrated consistency with experiment at the GW{sub 0}-BSE level. Deviations from experimental data are expected due to varying experimental conditions. Comparison of our results to spectroscopic ellipsometry data for realistic nanostructures has shown that although TDDFT may provide a computationally feasible level of theory in evaluation of the dielectric function, application is subject to validation with GW-BSE calculations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Molecular beam epitaxy growth and magnetic properties of Cr-Co-Ga Heusler alloy films

We have re-investigated growth and magnetic properties of Cr{sub 2}CoGa films using molecular beam epitaxy technique. Phase separation and precipitate formation were observed experimentally again in agreement with observation of multiple phases separation in sputtered Cr{sub 2}CoGa films by M. Meinert et al. However, significant phase separation could be suppressed by proper control of growth conditions. We showed that Cr{sub 2}CoGa Heusler phase, rather than Co{sub 2}CrGa phase, constitutes the majority of the sample grown on GaAs(001) at 450 {sup o}C. The measured small spin moment of Cr{sub 2}CoGa is in agreement with predicted HM-FCF nature; however, its Curie temperature is not as high as expected from the theoretical prediction probably due to the off-stoichiometry of Cr{sub 2}CoGa and the existence of the disorders and phase separation.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Thermodynamic analysis of tar reforming through auto-thermal reforming process

Fixed bed gasification is a simple and suitable technology for small scale power generation. One of the disadvantages of this technology is producing tar. So far, tar is not utilized yet and being waste that should be treated into a more useful product. This paper presents a thermodynamic analysis of tar conversion into gas producer through non-catalytic auto-thermal reforming technology. Tar was converted into components, C, H, O, N and S, and then reacted with oxidant such as mixture of air or pure oxygen. Thus, this reaction occurred auto-thermally and reached chemical equilibrium. The sensitivity analysis resulted that the most promising process performance occurred at flow rate of air was reached 43% of stoichiometry while temperature of process is 1100°C, the addition of pure oxygen is 40% and preheating of oxidant flow is 250°C. The yield of the most promising process performance between 11.15-11.17 kmol/h and cold gas efficiency was between 73.8-73.9%.The results of this study indicated that thermodynamically the conversion of tar into producer gas through non-catalytic auto-thermal reformingis more promising.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Two-dimensional percolation threshold in confined Si nanoparticle networks

Non-percolating and percolating silicon quantum dot (QD) networks were investigated by plane-view energy filtered transmission electron microscopy (EF-TEM). The Si QD networks were prepared by plasma enhanced chemical vapor deposition on free standing 5 nm Si{sub 3}N{sub 4} membranes, followed by high temperature annealing. The percolation threshold from non-percolating to percolating networks is found to be in between a SiO{sub x} stoichiometry of SiO{sub 0.5} up to SiO{sub 0.7}. Using the EF-TEM images, key structural parameters of the Si QD ensemble were extracted and compared, i.e., their size distribution, nearest neighbor distance, and circularity. Increasing the silicon excess within the SiO{sub x} layer results in an ensemble of closer spaced, less size-controlled, and less circular Si QDs that give rise to coupling effects. Furthermore, the influence of the structural parameters on the optical and electrical Si QD ensemble properties is discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Spectral identification scheme for epitaxially grown single-phase niobium dioxide

This publication describes how to distinguish under-oxidized and over-oxidized phases of the metal-insulator transition material NbO{sub 2} by employing a combination of the Nb 3d and O 1s core-level and valence-band spectra. Niobium oxides (NbO{sub x}) are grown under various conditions by molecular beam epitaxy on several different substrates, mostly (111)-oriented strontium titanate (SrTiO{sub 3}), in order to obtain phase-pure NbO{sub 2}. The films are characterized by in situ reflection high-energy electron diffraction, X-ray diffraction, and transmission electron microscopy to determine crystallinity, lattice constants, and epitaxial relationships. Niobium metal oxidation states and film stoichiometry are determined with in situ X-ray photoelectron spectroscopy. Asymmetric Nb 3d core-level spectral components are observed in phase-pure NbO{sub 2}, with a binding energy for Nb 3d{sub 5/2} of 206 eV. The effect of substrate type, growth temperature, and oxygen pressure on the film composition is also described.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Luminescence properties of Ce{sup 3+} and Tb{sup 3+} co-doped SiO{sub x}N{sub y} thin films: Prospects for color tunability in silicon-based hosts

In this work, the role of the nitrogen content, the annealing temperature, and the sample morphology on the luminescence properties of Ce{sup 3+} and Tb{sup 3+} co-doped SiO{sub x}N{sub y} thin films has been investigated. An increasing nitrogen atomic percentage has been incorporated in the host matrix by gradually replacing oxygen with nitrogen during fabrication while maintaining the Si content unaltered, obtaining a sequential variation in the film composition from nearly stoichiometric SiO{sub 2} to SiO{sub x}N{sub y}. The study of rare earth doped single layers has allowed us to identify the parameters that yield an optimum optical performance from Ce{sup 3+} and Tb{sup 3+} ions. Ce{sup 3+} ions proved to be highly sensitive to the annealing temperature and the nitrogen content, showing strong PL emission for relatively low nitrogen contents (from 0 to 20%) and moderate annealing temperatures (800–1000 °C) or under high temperature annealing (1180 °C). Tb{sup 3+} ions, on the other hand, displayed a mild dependence on those film parameters. Rare earth co-doping has also been investigated by comparing the luminescence properties of three different approaches: (i) a Ce{sup 3+} and Tb{sup 3+} co-doped SiO{sub x}N{sub y} single layer, (ii) a bilayer composed of two SiO{sub x}N{sub y} single layers doped with either Ce{sup 3+} or Tb{sup 3+} ions, and (iii) a multilayer composed of a series of either Tb{sup 3+} or Ce{sup 3+}-doped SiO{sub x}N{sub y} thin films with interleaved SiO{sub 2} spacers. Bright green emission and efficient energy transfer from either Ce{sup 3+} ions or Ce silicates to Tb{sup 3+} ions has been observed in the co-doped single layer as a consequence of the strong ion-ion interaction. On the other hand, independent luminescence from Ce{sup 3+} and Tb{sup 3+} ions has been observed in the Ce{sup 3+} and Tb{sup 3+} co-doped bilayer and multilayer, providing a good scenario to develop light emitting devices with wide color tunability by varying the number of deposited films that contain each rare earth dopant. Moreover, the optoelectronic properties of Ce{sup 3+}- and/or Tb{sup 3+}-doped thin films have been studied by depositing transparent conductive electrodes over selected samples. An electroluminescence signal according to the rare earth transitions is obtained in all cases, validating the excitation of Ce{sup 3+} and Tb{sup 3+} ions upon electron injection. Also, the main charge transport of injected electrons has been evaluated and correlated with the layer stoichiometry. Finally, a simple reliability test has allowed disclosing the origin of the early breakdown of test devices, attributed to the excessive joule heating at filament currents that occur around a region close to the polarization point.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Growth far from equilibrium: Examples from III-V semiconductors

The development of new applications has driven the field of materials design and synthesis to investigate materials that are not thermodynamically stable phases. Materials which are not thermodynamically stable can be synthesized and used in many applications. These materials are kinetically stabilized during use. The formation of such metastable materials requires both an understanding of the associated thermochemistry and the key surface transport processes present during growth. Phase separation is most easily accomplished at the growth surface during synthesis where mass transport is most rapid. These surface transport processes are sensitive to the surface stoichiometry, reconstruction, and chemistry as well as the growth temperature. The formation of new metastable semiconducting alloys with compositions deep within a compositional miscibility gap serves as model systems for the understanding of the surface chemical and physical processes controlling their formation. The GaAs{sub 1−y}Bi{sub y} system is used here to elucidate the role of surface chemistry in the formation of a homogeneous metastable composition during the chemical vapor deposition of the alloy system.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Structural and electronic properties of V{sub 2}O{sub 3} ultrathin film on Ag(001): LEED and photoemission study

V{sub 2}O{sub 3} ultrathin films were grown on Ag(001) substrate by reactive evaporation of vanadium (V) metal in presence of oxygen and their structural and electronic properties were studied by Low Energy Electron Diffraction (LEED), X-ray Photo Electron Spectroscopy (XPS) and Angle Resolved Photoemission Spectroscopic (ARPES) techniques, respectively. On top of square symmetry substrate Ag(001), hexagonal surface of V{sub 2}O{sub 3} (0001) is stabilized in the form of two domain structure, rotated by 30°(or 90°)to each other, has been observed by LEED. Rather than epitaxial flat monolayer, formation of well-ordered V{sub 2}O{sub 3} (0001) island has been confirmed from the LEED and the Photoemission Spectroscopic (PES) study. Stoichiometry of the grown film was confirmed by the XPS study. Evolution of valance band electronic structure of V{sub 2}O{sub 3} (0001) surface has been studied as a function of film thickness by ARPES.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Periodic surface structure bifurcation induced by ultrafast laser generated point defect diffusion in GaAs

The formation of high spatial frequency laser induced periodic surface structures (HSFL) with period <0.3 λ in GaAs after irradiation with femtosecond laser pulses in air is studied. We have identified a point defect generation mechanism that operates in a specific range of fluences in semiconductors between the band-gap closure and ultrafast-melt thresholds that produces vacancy/interstitial pairs. Stress relaxation, via diffusing defects, forms the 350–400 nm tall and ∼90 nm wide structures through a bifurcation process of lower spatial frequency surface structures. The resulting HSFL are predominately epitaxial single crystals and retain the original GaAs stoichiometry.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗