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At least 775 records · Page 43
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Indication of non-thermal contribution to visible femtosecond laser-induced CO oxidation on Ru(0001)

We studied CO oxidation on Ru(0001) induced by 400 nm and 800 nm femtosecond laser pulses where we find a branching ratio between CO oxidation and desorption of 1:9 and 1:31, respectively, showing higher selectivity towards CO oxidation for the shorter wavelength excitation. Activation energies computed with density functional theory show discrepancies with values extracted from the experiments, indicating both a mixture between different adsorbed phases and importance of non-adiabatic effects on the effective barrier for oxidation. We simulated the reactions using kinetic modeling based on the two-temperature model of laser-induced energy transfer in the substrate combined with a friction model for the coupling to adsorbate vibrations. This model gives an overall good agreement with experiment except for the substantial difference in yield ratio between CO oxidation and desorption at 400 nm and 800 nm. However, including also the initial, non-thermal effect of electrons transiently excited into antibonding states of the O-Ru bond yielded good agreement with all experimental results.

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

Diffusion coefficients of Fokker-Planck equation for rotating dust grains in a fusion plasma

In the fusion devices, ions, H atoms, and H{sub 2} molecules collide with dust grains and exert stochastic torques which lead to small variations in angular momentum of the grain. By considering adsorption of the colliding particles, thermal desorption of H atoms and normal H{sub 2} molecules, and desorption of the recombined H{sub 2} molecules from the surface of an oblate spheroidal grain, we obtain diffusion coefficients of the Fokker-Planck equation for the distribution function of fluctuating angular momentum. Torque coefficients corresponding to the recombination mechanism show that the nonspherical dust grains may rotate with a suprathermal angular velocity.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

Annealing effect on thermodynamic and physical properties of mesoporous silicon: A simulation and nitrogen sorption study

Discovery of porous silicon formation in silicon substrate in 1956 while electro-polishing crystalline Si in hydrofluoric acid (HF), has triggered large scale investigations of porous silicon formation and their changes in physical and chemical properties with thermal and chemical treatment. A nitrogen sorption study is used to investigate the effect of thermal annealing on electrochemically etched mesoporous silicon (PS). The PS was thermally annealed from 200°C to 800°C for 1 hr in the presence of air. It was shown that the pore diameter and porosity of PS vary with annealing temperature. The experimentally obtained adsorption / desorption isotherms show hysteresis typical for capillary condensation in porous materials. A simulation study based on Saam and Cole model was performed and compared with experimentally observed sorption isotherms to study the physics behind of hysteresis formation. We discuss the shape of the hysteresis loops in the framework of the morphology of the layers. The different behavior of adsorption and desorption of nitrogen in PS with pore diameter was discussed in terms of concave menisci formation inside the pore space, which was shown to related with the induced pressure in varying the pore diameter from 7.2 nm to 3.4 nm.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Enhanced flashover strength in polyethylene nanodielectrics by secondary electron emission modification

This work studies the correlation between secondary electron emission (SEE) characteristics and impulse surface flashover in polyethylene nanodielectrics both theoretically and experimentally, and illustrates the enhancement of flashover voltage in low-density polyethylene (LDPE) through incorporating Al{sub 2}O{sub 3} nanoparticles. SEE characteristics play key roles in surface charging and gas desorption during surface flashover. This work demonstrates that the presence of Al{sub 2}O{sub 3} nanoparticles decreases the SEE coefficient of LDPE and enhances the impact energy at the equilibrium state of surface charging. These changes can be explained by the increase of surface roughness and of surface ionization energy, and the strong interaction between nanoparticles and the polymer dielectric matrix. The surface charge and flashover voltage are calculated according to the secondary electron emission avalanche (SEEA) model, which reveals that the positive surface charges are reduced near the cathode triple point, while the presence of more nanoparticles in high loading samples enhances the gas desorption. Consequently, the surface flashover performance of LDPE/Al{sub 2}O{sub 3} nanodielectrics is improved.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

Development of contamination-free x-ray optics for next-generation light sources

We studied typical forms of contamination on X-ray mirrors that cause degradation of beam quality, investigated techniques to remove the contaminants, and propose methods to eliminate the sources of the contamination. The total amount of carbon-containing substances on various materials in the vicinity of a mirror was measured by thermal desorption-gas chromatography/mass spectrometry and thermal desorption spectroscopy. It was found that cleanliness and ultra-high vacuum techniques are required to produce the contamination-free surfaces that are essential for the propagation of high-quality X-ray beams. The reduction of carbonaceous residue adsorbed on the surfaces, and absorbed into the bulk, of the materials in the vicinity of the mirrors is a key step toward achieving contamination-free X-ray optics.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2016

High voltage threshold for stable operation in a dc electron gun

We report clear observation of a high voltage (HV) threshold for stable operation in a dc electron gun. The HV hold-off time without any discharge is longer than many hours for operation below the threshold, while it is roughly 10 min above the threshold. The HV threshold corresponds to the minimum voltage where discharge ceases. The threshold increases with the number of discharges during HV conditioning of the gun. Above the threshold, the amount of gas desorption per discharge increases linearly with the voltage difference from the threshold. The present experimental observations can be explained by an avalanche discharge model based on the interplay between electron stimulated desorption (ESD) from the anode surface and subsequent secondary electron emission from the cathode by the impact of ionic components of the ESD molecules or atoms.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2013

A UNIFIED MONTE CARLO TREATMENT OF GAS-GRAIN CHEMISTRY FOR LARGE REACTION NETWORKS. II. A MULTIPHASE GAS-SURFACE-LAYERED BULK MODEL

The observed gas-phase molecular inventory of hot cores is believed to be significantly impacted by the products of chemistry in interstellar ices. In this study, we report the construction of a full macroscopic Monte Carlo model of both the gas-phase chemistry and the chemistry occurring in the icy mantles of interstellar grains. Our model treats icy grain mantles in a layer-by-layer manner, which incorporates laboratory data on ice desorption correctly. The ice treatment includes a distinction between a reactive ice surface and an inert bulk. The treatment also distinguishes between zeroth- and first-order desorption, and includes the entrapment of volatile species in more refractory ice mantles. We apply the model to the investigation of the chemistry in hot cores, in which a thick ice mantle built up during the previous cold phase of protostellar evolution undergoes surface reactions and is eventually evaporated. For the first time, the impact of a detailed multilayer approach to grain mantle formation on the warm-up chemistry is explored. The use of a multilayer ice structure has a mixed impact on the abundances of organic species formed during the warm-up phase. For example, the abundance of gaseous HCOOCH{sub 3} is lower in the multilayer model than in previous grain models that do not distinguish between layers (so-called two phase models). Other gaseous organic species formed in the warm-up phase are affected slightly. Finally, we find that the entrapment of volatile species in water ice can explain the two-jump behavior of H{sub 2}CO previously found in observations of protostars.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2013

Indirect ultraviolet photodesorption from CO:N{sub 2} binary ices — an efficient grain-gas process

Ultraviolet (UV) ice photodesorption is an important non-thermal desorption pathway in many interstellar environments that has been invoked to explain observations of cold molecules in disks, clouds, and cloud cores. Systematic laboratory studies of the photodesorption rates, between 7 and 14 eV, from CO:N{sub 2} binary ices, have been performed at the DESIRS vacuum UV beamline of the synchrotron facility SOLEIL. The photodesorption spectral analysis demonstrates that the photodesorption process is indirect, i.e., the desorption is induced by a photon absorption in sub-surface molecular layers, while only surface molecules are actually desorbing. The photodesorption spectra of CO and N{sub 2} in binary ices therefore depend on the absorption spectra of the dominant species in the sub-surface ice layer, which implies that the photodesorption efficiency and energy dependence are dramatically different for mixed and layered ices compared with pure ices. In particular, a thin (1-2 ML) N{sub 2} ice layer on top of CO will effectively quench CO photodesorption, while enhancing N{sub 2} photodesorption by a factor of a few (compared with the pure ices) when the ice is exposed to a typical dark cloud UV field, which may help to explain the different distributions of CO and N{sub 2}H{sup +} in molecular cloud cores. This indirect photodesorption mechanism may also explain observations of small amounts of complex organics in cold interstellar environments.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

Experiments of water formation on warm silicates

When dust grains have a higher temperature than they would have in dense clouds, and when H, H{sub 2}, and O{sub 2} have a negligible residence time on grains, the formation of water should still be possible via the hydrogenation of OH and Eley-Rideal-type reactions. We determined that the OH desorption energy from an amorphous silicate surface is at least 143 meV (1656 K). This is 400 K higher than the value previously used in chemical models of the interstellar medium and is possibly as high as 410 meV (4760 K). This extends the temperature range for the efficient formation of water on grains from about 30 K to at least 50 K, and possibly over 100 K. We do not find evidence that water molecules leave the surface upon formation. Instead, through a thermal programmed desorption experiment, we find that water formed on the surface of an amorphous silicate desorbs at around 160 K. We also measured the cross-sections for the reaction of H and D with an O{sub 3} layer on an amorphous silicate surface at 50 K. The values of the cross-sections, σ{sub H} = 1.6 ± 0.27 Å{sup 2} and σ{sub D} = 0.94 ± 0.09 Å{sup 2}, respectively, are smaller than the size of an O{sub 3} molecule, suggesting the reaction mechanism is more likely Eley-Rideal than hot-atom. Information obtained through these experiments should help theorists evaluate the relative contribution of water formation on warm grains versus in the gas phase.

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

EVAPORATION OF GRAIN-SURFACE SPECIES BY SHOCK WAVES IN A PROTOPLANETARY DISK

Recent Atacama Large Millimeter/submillimeter Array observations of young protostellar objects detected warm SO emission, which could be associated with a forming protostellar disk. In order to investigate if such warm gas can be produced by accretion shock onto the forming disk, we calculate the sputtering and thermal desorption of various grain-surface species in one-dimensional shock waves. We find that thermal desorption is much more efficient than the sputtering in the post-shock region. While H{sub 2}O can be thermally desorbed, if the accretion velocity is larger than 8 km s{sup –1} with the pre-shock gas number density of 10{sup 9} cm{sup –3}, SO is desorbed if the accretion velocity ≳2 km s{sup –1} and ≳4 km s{sup –1}, with the pre-shock density of 10{sup 9} cm{sup –3} and 10{sup 8} cm{sup –3}, respectively. We also find that the column density of hydrogen nuclei in warm post-shock gas is N {sub warm} ∼ 10{sup 21} cm{sup –2}.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2011

Correlating Titania Morphology and Chemical Composition with Dye-sensitized Solar Cell Performance

We have investigated the use of various morphologies, including nanoparticles, nanowires, and sea-urchins of TiO{sub 2} as the semiconducting material used as components of dye-sensitized solar cells (DSSCs). Analysis of the solar cells under AM 1.5 solar irradiation reveals the superior performance of hydrothermally derived nanoparticles, by comparison with two readily available commercial nanoparticle materials, within the DSSC architecture. The sub-structural morphology of films of these nanostructured materials has been directly characterized using SEM and indirectly probed using dye desorption. Furthermore, the surfaces of these nanomaterials were studied using TEM in order to visualize their structure, prior to their application within DSSCs. Surface areas of the materials have been quantitatively analyzed by collecting BET adsorption and dye desorption data. Additional investigation using open circuit voltage decay measurements reveals the efficiency of electron conduction through each TiO{sub 2} material. Moreover, the utilization of various chemically distinctive titanate materials within the DSSCs has also been investigated, demonstrating the deficiencies of using these particular chemical compositions within traditional DSSCs.

14 SOLAR ENERGY↗
DOE OSTI2012

Role of surface temperature in fluorocarbon plasma-surface interactions

This article examines plasma-surface reaction channels and the effect of surface temperature on the magnitude of those channels. Neutral species CF{sub 4}, C{sub 2}F{sub 6}, and C{sub 3}F{sub 8} are produced on surfaces. The magnitude of the production channel increases with surface temperature for all species, but favors higher mass species as the temperature is elevated. Additionally, the production rate of CF{sub 2} increases by a factor of 5 as the surface temperature is raised from 25 Degree-Sign C to 200 Degree-Sign C. Fluorine density, on the other hand, does not change as a function of either surface temperature or position outside of the plasma glow. This indicates that fluorine addition in the gas-phase is not a dominant reaction. Heating reactors can result in higher densities of depositing radical species, resulting in increased deposition rates on cooled substrates. Finally, the sticking probability of the depositing free radical species does not change as a function of surface temperature. Instead, the surface temperature acts together with an etchant species (possibly fluorine) to elevate desorption rates on that surface at temperatures lower than those required for unassisted thermal desorption.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2013

High temperature growth of Ag phases on Ge(111)

The growth of the (3 Multiplication-Sign 1) and ({radical}3 Multiplication-Sign {radical}3)R30 Degree-Sign phases of Ag on Ge(111) on substrates at temperatures from 540 to 660 Degree-Sign C is characterized with low energy electron microscopy (LEEM) and low energy electron diffraction (LEED). From 540 Degree-Sign C to the Ag desorption temperature of 575 Degree-Sign C, LEEM images show that growth of the (3 Multiplication-Sign 1) phase begins at step edges. Upon completion of the (3 Multiplication-Sign 1) phase, the ({radical}3 Multiplication-Sign {radical}3)R30 Degree-Sign phase is observed with a dendritic growth morphology that is not much affected by steps. For sufficiently high deposition rates, Ag accumulates on the sample above the desorption temperature. From 575 to 640 Degree-Sign C, the growth proceeded in a manner similar to that at lower temperatures, with growth of the (3 Multiplication-Sign 1) phase to completion, followed by growth of the ({radical}3 Multiplication-Sign {radical}3)R30 Degree-Sign phase. Increasing the substrate temperature to 660 Degree-Sign C resulted in only (3 Multiplication-Sign 1) growth. In addition, for samples with Ag coverage less than 0.375ML, LEEM and LEED images were used to follow a reversible phase transformation near 575 Degree-Sign C, between a mixed high coverage phase of [(4 Multiplication-Sign 4) + (3 Multiplication-Sign 1)] and the high temperature, lower coverage (3 Multiplication-Sign 1) phase.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Non-Arrhenius temperature dependence of the island density of one-dimensional Al chains on Si(100): A kinetic Monte Carlo study

Classical nucleation theory predicts that the evolution of mean island density with temperature during growth in one-dimensional systems obeys the Arrhenius relation. In this study, kinetic Monte Carlo simulations of a suitable atomistic lattice-gas model were performed to investigate the experimentally observed non-Arrhenius scaling behavior of island density in the case of one-dimensional Al islands grown on Si(100). Previously, it was proposed that adatom desorption resulted in a transition temperature signaling the departure from classical predictions. Here, the authors demonstrate that desorption above the transition temperature is not possible. Instead, the authors posit that the existence of a transition temperature is due to a combination of factors such as reversibility of island growth, presence of C-defects, adatom diffusion rates, as well as detachment rates at island ends. In addition, the authors show that the anomalous non-Arrhenius behavior vanishes when adatom binds irreversibly with C-defects as observed in In on Si(100) studies.

42 ENGINEERING↗
DOE OSTI2016

Optimizing AlF{sub 3} atomic layer deposition using trimethylaluminum and TaF{sub 5}: Application to high voltage Li-ion battery cathodes

Atomic layer deposition (ALD) of conformal AlF{sub 3} coatings onto both flat silicon substrates and high-voltage LiNi{sub 0.5}Mn{sub 0.3}Co{sub 0.2}O{sub 2} (NMC) Li-ion battery cathode powders was investigated using a Al(CH{sub 3}){sub 3}/TaF{sub 5} precursor combination. This optimized approach employs easily handled ALD precursors, while also obviating the use of highly toxic HF(g). In studies conducted on planar Si wafers, the film's growth mode was dictated by a competition between the desorption and decomposition of Ta reaction byproducts. At T ≥ 200 °C, a rapid decomposition of the Ta reaction byproducts to TaC led to continuous deposition and high concentrations of TaC in the films. A self-limited ALD growth mode was found to occur when the deposition temperature was reduced to 125 °C, and the TaF{sub 5} exposures were followed by an extended purge. The lower temperature process suppressed conversion of TaF{sub x}(CH{sub 3}){sub 5−x} to nonvolatile TaC, and the long purges enabled nearly complete TaF{sub x}(CH{sub 3}){sub 5−x} desorption, leaving behind the AlF{sub 3} thin films. NMC cathode powders were coated using these optimized conditions, and coin cells employing these coated cathode particles exhibited significant improvements in charge capacity fade at high discharge rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Effect of high-energy electron irradiation in an electron microscope column on fluorides of alkaline earth elements (CaF{sub 2}, SrF{sub 2}, and BaF{sub 2})

The effect of high-energy (150 eV) electron irradiation in an electron microscope column on crystals of fluorides of alkaline earth elements CaF{sub 2}, SrF{sub 2}, and BaF{sub 2} is studied. During structural investigations by electron diffraction and electron microscopy, the electron irradiation causes chemical changes in MF{sub 2} crystals such as the desorption of fluorine and the accumulation of oxygen in the irradiated area with the formation of oxide MO. The fluorine desorption rate increases significantly when the electron-beam density exceeds the threshold value of {approx}2 Multiplication-Sign 10{sup 3} pA/cm{sup 2}). In BaF{sub 2} samples, the transformation of BaO into Ba(OH){sub 2} was observed when irradiation stopped. The renewal of irradiation is accompanied by the inverse transformation of Ba(OH){sub 2} into BaO. In the initial stage of irradiation of all MF{sub 2} compounds, the oxide phase is in the single-crystal state with a lattice highly matched with the MF{sub 2} matrix. When the irradiation dose is increased, the oxide phase passes to the polycrystalline phase. Gaseous products of MF{sub 2} destruction (in the form of bubbles several nanometers in diameter) form a rectangular array with a period of {approx}20 nm in the sample.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2011

Loss of hydrogen atoms in H{sub 2} plasma on the surfaces of materials used in EUV lithography

Low-pressure hydrogen is an important component of the working medium in extreme ultraviolet (EUV) projection lithography. Under the action of EUV photons and fast secondary electrons on the gas medium, plasma and atomic hydrogen, actively interacting with the surface, are produced. This interaction is very important, because it largely determines the lifetime of the multilayered EUV optics. In this study, the loss of atomic hydrogen under the conditions of a low pressure (<10 Torr) RF plasma discharge on the surfaces of materials used in EUV lithography is investigated. The surface loss probabilities of H atoms on these materials are measured. It is shown that surface recombination of atomic hydrogen goes according to the Eley-Rideal mechanism via direct recombination of H atoms from the gas phase with chemically and physically adsorbed atoms. In this case, the surface recombination probability is mainly determined by the density of chemical adsorption sites. The density of adsorption sites and the desorption energy of H atoms are estimated. The desorption energy of physically adsorbed H atoms on pure metal surfaces (or surfaces exposed to plasma) is about 0.5 eV, and the density of sorption sites is close to the surface density of atoms. This results in a high loss probability of H atoms on metals ({approx}0.1). Therefore, to provide efficient transportation of hydrogen atoms, it is necessary to use materials with the lowest loss probability of H atoms, i.e., dielectrics.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2015

In-situ observation of sputtered particles for carbon implanted tungsten during energetic isotope ion implantation

Tungsten is a candidate for plasma facing materials in future fusion reactors. During DT plasma operations, carbon as an impurity will bombard tungsten, leading to the formation of tungsten-carbon (WC) layer and affecting tritium recycling behavior. The effect of carbon implantation for the dynamic recycling of deuterium, which demonstrates tritium recycling, including retention and sputtering, has been investigated using in-situ sputtered particle measurements. The C{sup +} implanted W, WC and HOPG were prepared and dynamic sputtered particles were measured during H{sub 2}{sup +} irradiation. It has been found that the major hydrocarbon species for C{sup +} implanted tungsten is CH{sub 3}, while for WC and HOPG (Highly Oriented Pyrolytic Graphite) it is CH{sub 4}. The chemical state of hydrocarbon is controlled by the H concentration in a W-C mixed layer. The amount of C-H bond and the retention of H trapped by carbon atom should control the chemical form of hydrocarbon sputtered by H{sub 2}{sup +} irradiation and the desorption of CH{sub 3} and CH{sub 2} are due to chemical sputtering, although that for CH is physical sputtering. The activation energy for CH{sub 3} desorption has been estimated to be 0.4 eV, corresponding to the trapping process of hydrogen by carbon through the diffusion in W. It is concluded that the chemical states of hydrocarbon sputtered by H{sub 2}{sup +} irradiation for W is determined by the amount of C-H bond on the W surface. (authors)

36 MATERIALS SCIENCE↗