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At least 523 records · Page 29

Enhanced surface transfer doping of diamond by V{sub 2}O{sub 5} with improved thermal stability

Surface transfer doping of hydrogen-terminated diamond has been achieved utilising V{sub 2}O{sub 5} as a surface electron accepting material. Contact between the oxide and diamond surface promotes the transfer of electrons from the diamond into the V{sub 2}O{sub 5} as revealed by the synchrotron-based high resolution photoemission spectroscopy. Electrical characterization by Hall measurement performed before and after V{sub 2}O{sub 5} deposition shows an increase in hole carrier concentration in the diamond from 3.0 × 10{sup 12} to 1.8 × 10{sup 13 }cm{sup −2} at room temperature. High temperature Hall measurements performed up to 300 °C in atmosphere reveal greatly enhanced thermal stability of the hole channel produced using V{sub 2}O{sub 5} in comparison with an air-induced surface conduction channel. Transfer doping of hydrogen-terminated diamond using high electron affinity oxides such as V{sub 2}O{sub 5} is a promising approach for achieving thermally stable, high performance diamond based devices in comparison with air-induced surface transfer doping.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Atomic scale study of surface orientations and energies of Ti 2 O 3 crystals

For nanostructured particles, the faceting planes and their terminating chemical species are two critical factors that govern their chemical behavior. In this paper, the surface atomistic structure and termination of Ti 2 O 3 crystals were analyzed using atomic-scale aberration-corrected scanning transmission electron microscopy (STEM) combined with density functional theory (DFT) calculations. STEM imaging reveals that the Ti 2 O 3 crystals are most often faceted along (001), (012), (-114), and (1–20) planes. The DFT calculation indicates that the (012) surface with TiO-termination has the lowest cleavage energy and correspondingly the lowest surface energy, indicating that (012) will be the most stable and prevalent surfaces in Ti 2 O 3 nanocrystals. Finally, these observations provide insights for exploring the interfacial process involving Ti 2 O 3 nanoparticles.

36 MATERIALS SCIENCE↗

Critical velocity phenomena and the LTP

When the relative velocity between magnetized plasma and neutral gas exceeds a critical value, the gas-plasma interaction is dominated by collective phenomena which rapidly excite and ionize the neutrals. The interaction of the solar wind with a large cloud (between 10 to the 24th and 10 to the 28th power neutrals) vented from the moon should be of this type. Line radiation from such an interaction can yield an apparent lunar surface brightness rivaling reflected sunlight levels over small areas, if the kinetic-energy flow density of the gas is sufficiently high. The aberrated solar-wind flow past the moon would enhance the visibility of such interactions near the lunar sunrise terminator, supporting the statistical studies which indicate that the 'Lunar Transient Phenomena' (anomalous optical phenomena on the moon) are significantly correlated with the position of the terminator on the lunar surface.

Srnka, L. J.↗

A Study of an Optical Lunar Surface Communications Network with High Bandwidth Direct to Earth Link

A lunar surface systems study explores the application of optical communications to support a high bandwidth data link from a lunar relay satellite and from fixed lunar assets. The results show that existing 1-m ground stations could provide more than 99% coverage of the lunar terminal at 100Mb/s data rates from a lunar relay satellite and in excess of 200Mb/s from a fixed terminal on the lunar surface. We have looked at the effects of the lunar regolith and its removal on optical samples. Our results indicate that under repeated dust removal episodes sapphire rather than fused silica would be a more durable material for optical surfaces. Disruption tolerant network protocols can minimize the data loss due to link dropouts. We report on the preliminary results of the DTN protocol implemented over the optical carrier.

lunar optical communications↗

Surface-functionalized silicon anode for high energy lithium ion batteries

A composition includes a silicon nanoparticle having surface-attached groups, and the silicon nanoparticle is represented by the formula: [Si]-[linker]-[terminal group]. In the formula [Si] represents the surface of the silicon nanoparticle; [terminal group] is a moiety that is configured for further reaction or is compatible with the electrolyte; and [linker] is a group linking the surface of the silicon nanoparticle to the [terminal group].

Zhang, Zhengcheng↗

By-controlled convection and field-aligned currents near midnight auroral oval for northward interplanetary magnetic field

Using the Dynamics Explorer (DE) 2 magnetic and electric field and plasma data, B(sub y)- controlled convection and field-aligned currents in the midnight sector for northward interplanetary magnetic field (IMF) are examined. The results of an analysis of the electric field data show that when IMF is stable and when its magnitude is large, a coherent B(sub y)-controlled convection exists near the midnight auroral oval in the ionosphere having adequate conductivities. When B(sub y) is negative, the convection consists of a westward (eastward) plasma flow at the lower latitudes and an eastward (westward) plasma flow at the higher latitudes in the midnight sector in the northern (southern) ionosphere. When B(sub y) is positive, the flow directions are reversed. The distribution of the field-aligned currents associated with the B(sub y)-controlled convection, in most cases, shows a three-sheet structure. In accordance with the convection the directions of the three sheets are dependent on the sign of B(sub y). The location of disappearance of the precipitating intense electrons having energies of a few keV is close to the convection reversal surface. However, the more detailed relationship between the electron precipitation boundary and the convection reversal surface depends on the case. In some cases the precipitating electrons extend beyond the convection reversal surface, and in others the poleward boundary terminates at a latitude lower than the reversal surface. Previous studies suggest that the poleward boundary of the electrons having energies of a few keV is not necessarily coincident with an open/closed bounary. Thus the open/closed boundary may be at a latitude higher than the poleward boundary of the electron precipitation, or it may be at a latitude lower than the poleward boundary of the electron precipitation. We discuss relationships between the open/closed boundary and the convection reversal surface. When as a possible choice we adopt a view that the open/closed boundary agrees with the convection reversal surface, we can explain qualitatively the configuration of the B(sub y)-controlled convection on the open and close field line regions by proposing a mapping modified in accordance with IMF B(sub y).

Taguchi, S.↗

Enhancement to the conductivity of surface transfer-doped (111) diamond through thermochemical surface etching

The use of a transition metal catalyzed thermochemical etching method for improving the carrier transport properties of the near-surface two-dimensional (2D) hole gas in surface transfer-doped hydrogen-terminated (111) diamond is demonstrated. Using Ni 0.8 Cr 0.2 films deposited and annealed to a temperature of 900 °C, with up to three etch cycles, preferential (111) surface etching produces large terraces exceeding 10 μm in size with a surface microroughness, σ 2 RMS λ, that is two orders of magnitude lower than for the pre-etched (111) surface. Magnetotransport measurements on hydrogen-terminated Hall bars engineered on the pre- and post-etched surfaces and rendered conductive by the adsorbed water layer formed on exposure to ambient conditions demonstrate that this etching causes an improvement in the hole mobility by an order of magnitude, resulting in a measured sheet resistivity of 1.04 kΩ/sq at a temperature of 4.2 K without gating.

42 ENGINEERING↗

Distributed modeling of ablation (1996–2011) and climate sensitivity on the glaciers of Taylor Valley, Antarctica

Here, the McMurdo Dry Valleys of Antarctica host the coldest and driest ecosystem on Earth, which is acutely sensitive to the availability of water coming from glacial runoff. We modeled the spatial variability in ablation and assessed climate sensitivity of the glacier ablation zones using 16 years of meteorological and surface mass-balance observations collected in Taylor Valley. Sublimation was the primary form of mass loss over much of the ablation zones, except for near the termini where melt, primarily below the surface, dominated. Microclimates in ~10 m scale topographic basins generated melt rates up to ten times higher than over smooth glacier surfaces. In contrast, the vertical terminal cliffs on the glaciers can have higher or lower melt rates than the horizontal surfaces due to differences in incoming solar radiation. The model systematically underpredicted ablation for the final 5 years studied, possibly due to an increase of windblown sediment. Surface mass-balance sensitivity to temperature was ~–0.02 m w.e. K –1 , which is among the smallest magnitudes observed globally. We also identified a high sensitivity to ice albedo, with a decrease of 0.02 having similar effects as a 1 K increase in temperature, and a complex sensitivity to wind speed.

54 ENVIRONMENTAL SCIENCES↗

Vanadate Retention by Iron and Manganese Oxides

Anthropogenic emissions of vanadium (V) into terrestrial and aquatic surface systems now match those of geogenic processes, and yet, the geochemistry of vanadium is poorly described in comparison to other comparable contaminants like arsenic. In oxic systems, V is present as an oxyanion with a +5 formal charge on the V center, typically described as H x VO 4 (3–x)– , but also here as V(V). Iron (Fe) and manganese (Mn) (oxy)hydroxides represent key mineral phases in the cycling of V(V) at the solid–solution interface, and yet, fundamental descriptions of these surface-processes are not available. Here, we utilize extended X-ray absorption fine structure (EXAFS) and thermodynamic calculations to compare the surface complexation of V(V) by the common Fe and Mn mineral phases ferrihydrite, hematite, goethite, birnessite, and pyrolusite at pH 7. Inner-sphere V(V) complexes were detected on all phases, with mononuclear V(V) species dominating the adsorbed species distribution. Our results demonstrate that V(V) adsorption is exergonic for a variety of surfaces with differing amounts of terminal –OH groups and metal–O bond saturations, implicating the conjunctive role of varied mineral surfaces in controlling the mobility and fate of V(V) in terrestrial and aquatic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carboxylic acid ligand substituent impacts hydrosilylation activity of platinum single atom catalysts on ceria

Current industrially employed hydrosilylation catalysts rely on homogeneous platinum catalysts which are not recovered after the reaction. To eliminate this issue, our group has been working to optimize recyclability of heterogeneous platinum single atom catalysts (SACs) on ceria via 1,10-phenanthroline-5,6-dione ligands (PDO), which incorporates mono (PDO-C) and dicarboxylic acid (PDO-C2) groups in the 2- and 9-position of PDO ligand to increase metal–surface interaction. DRIFTS results confirm carboxylic acid coordination to the terminal hydroxy groups of the ceria surface. New catalyst synthesis conditions wherein PDO was combined with the metal prior to exposure to the surface allow control of Pt oxidation state on the surface. Here, the highest metal loading was observed for PDO and PDO-C, correlating with improved catalytic recyclability compared to the PDO-C2 ligand. It is proposed that the location of the carboxylic acid groups and the steric effects can explain the lower activity and metal loading for PDO-C2 ligands. Post-reaction XPS and DRIFTS spectra show the appearance of new Si and O species on the catalyst during the hydrosilylation reaction, indicating the silane reagent is depositing on the surface. The silane coverage and leaching of catalyst from the surface is the cause for the reduced catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Computational Investigation on Hydrodeoxygenation (HDO) of Acetone to Propylene on α-MoO 3 (010) Surface

Density functional theory (DFT) calculations were performed on the multistep hydrodeoxygenation (HDO) of acetone (CH 3 COCH 3 ) to propylene (CH 3 CHCH 2 ) on a molybdenum oxide (α-MoO 3 ) catalyst following an oxygen vacancy-driven pathway. First, a perfect O-terminated α-MoO 3 (010) surface based on a 4 × 2 × 4 supercell is reduced by molecular hydrogen (H 2 ) to generate a terminal oxygen (O t ) defect site. This process occurs via a dissociative chemisorption of H 2 on adjacent surface oxygen atoms, followed by an H transfer to form a water molecule (H 2 O). Next, adsorption of CH 3 COCH 3 on the oxygen-deficient Mo site forms an O–Mo bond and then the chemisorbed CH 3 COCH 3 forms CH 3 COCH 2 by transfer of an H atom to an adjacent O t site. The surface bound hydroxyl (OH) then transfers the H atom to the immobilized O atom to form surface-bound enol, CH 3 CHOCH 2 . The next step releases CH 3 CHCH 2 into the gas phase, while simultaneously oxidizes the surface back to a perfect O-terminated α-MoO 3 (010) surface. The adsorption of H 2 , and the formation of a terminal oxygen (Ot) vacancy, moves the conduction band minimum (CBM) from 1.2 eV to 0 and 0.3 eV, respectively. Climbing image-nudged elastic band (CI-NEB) calculations using a Perdew–Burke–Ernzerhof (PBE) functional in combination with double-ζ valence (DZV) basis sets indicate that the dissociative adsorption of H 2 is the rate-limiting step for the catalytic cycle with a barrier of 1.70 eV. Furthermore, the lower barrier for surface-mediated H transfer from primary-to-secondary carbon atom (0.63 eV) compared to that of a concerted direct H transfer to the secondary C atom with simultaneous desorption (2.02 eV) emphasizes the key role played by the surface in H transfer for effective deoxygenation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface Pyroelectricity in Cubic SrTiO 3

Symmetry-imposed restrictions on the number of available pyroelectric and piezoelectric materials remain a major limitation as 22 out of 32 crystallographic material classes exhibit neither pyroelectricity nor piezoelectricity. Yet, by breaking the lattice symmetry it is possible to circumvent this limitation. Here, using a unique technique for measuring transient currents upon rapid heating, direct experimental evidence is provided that despite the fact that bulk SrTiO 3 is not pyroelectric, the (100) surface of TiO 2 -terminated SrTiO 3 is intrinsically pyroelectric at room temperature. The pyroelectric layer is found to be ≈1 nm thick and, surprisingly, its polarization is comparable with that of strongly polar materials such as BaTiO 3 . The pyroelectric effect can be tuned ON/OFF by the formation or removal of a nanometric SiO 2 layer. Using density functional theory, the pyroelectricity is found to be a result of polar surface relaxation, which can be suppressed by varying the lattice symmetry breaking using a SiO 2 capping layer. The observation of pyroelectricity emerging at the SrTiO 3 surface also implies that it is intrinsically piezoelectric. Furthermore, these findings may pave the way for observing and tailoring piezo- and pyroelectricity in any material through appropriate breaking of symmetry at surfaces and artificial nanostructures such as heterointerfaces and superlattices.

30 DIRECT ENERGY CONVERSION↗

Proximity Operations for the Robotic Boulder Capture Option for the Asteroid Redirect Mission

In September of 2013, the Asteroid Robotic Redirect Mission (ARRM) Option B team was formed to expand on NASA's previous work on the robotic boulder capture option. While the original Option A concept focuses on capturing an entire smaller Near-Earth Asteroid (NEA) using an inflatable bag capture mechanism, this design seeks to land on a larger NEA and retrieve a boulder off of its surface. The Option B team has developed a detailed and feasible mission concept that preserves many aspects of Option A's vehicle design while employing a fundamentally different technique for returning a significant quantity of asteroidal material to the Earth-Moon system. As part of this effort, a point of departure proximity operations concept was developed complete with a detailed timeline, as well as DeltaV and propellant allocations. Special attention was paid to the development of the approach strategy, terminal descent to the surface, controlled ascent with the captured boulder, and control during the Enhanced Gravity Tractor planetary defense demonstration. The concept of retrieving a boulder from the surface of an asteroid and demonstrating the Enhanced Gravity Tractor planetary defense technique is found to be feasible and within the proposed capabilities of the Asteroid Redirect Vehicle (ARV). While this point of departure concept initially focuses on a mission to Itokawa, the proximity operations design is also shown to be extensible to wide range of asteroids.

Reeves, David M.↗

Promotion of CaCO 3 Nucleation by Carboxyl- and Amine-Terminated Peptoid Nanotubes

The use of surfaces to promote heterogeneous nucleation of CaCO 3 has been extensively studied to better understand natural processes of biomineralization, to develop bioinspired approaches for synthesizing composite materials with diverse functionalities, and as a route toward accelerating CO 2 mineralization. Peptoids have emerged as a material of particular interest, because they offer tunable side chain chemistry while maintaining a constant long-range self-assembled architecture. Here, in this work, we investigate the ability of films of self-assembled -NH 2 and −COOH terminated peptoid nanotubes to promote the nucleation of CaCO 3 . Using a combination of atomic force, scanning electron, and optical microscopy, we find that interwoven films of nanotubes formed from peptoids with -NH 2 side chains promote the preferential formation of vaterite with the (001) plane parallel to the film and exhibit a lower interfacial energy than that reported for inorganic surfaces. In contrast, the film of −COOH-functionalized peptoid nanotubes is a much stronger promoter, giving a particle density 5 orders of magnitude larger than for the -NH 2 terminated peptoid nanotubes and enabling complete coverage of individual peptoid tubes with CaCO 3 nanoparticles that results in a composite material with a 50-fold increase in Young’s modulus. Thus, interwoven films of peptoid nanotubes provide a useful platform for investigating the impact of specific chemical groups on nucleation and offer potential application to accelerated mineralization of CO 2 for removal from the environment or modulation of mineralogy and properties of carbonate-based building materials.

carbon nanotubes↗

Cosmogenic 10Be constraints on deglacial snowline rise in the Southern Alps, New Zealand

We report geochronological dating of glacial landforms, such as terminal and lateral moraines, is useful for determining the extent and timing of past glaciation and for reconstructing the magnitude and rate of past climate changes. In the Southern Alps of New Zealand, well-dated glacial geomorphological records constrain the last glacial cycle across much of the Waitaki River basin (e.g. Ōhau, Pukaki, Tekapo) but its southern sector such as the Ahuriri River valley remains comparatively unconstrained. Recently, there has been debate on the scale and rapidity of mountain glacier retreat during the last glacial termination, particularly the 20–17 ka period in New Zealand. Missing from this debate is well-constrained equilibrium-line altitude (ELA) and associated temperature reconstructions, particularly over the period around 17 ka, which can help us to develop a more complete picture of how past temperature changes drove glacier retreat. Here we report the first glacial chronology dataset from the Last Glacial Maximum (LGM) and subsequent deglaciation from the Ahuriri River valley, Southern Alps, New Zealand (44°23'54"S, 169°39'48"E) based on 38 beryllium-10 ( 10 Be) surface-exposure ages from terminal moraine systems and glaciated bedrock situated at the lower and middle sections of the valley. Our results show that the former Ahuriri Glacier reached its maximum extent at 19.8 ± 0.3 ka, which coincides with the global Last Glacial Maximum. By 16.7 ± 0.3 ka, the glacier had retreat ~18 km up-valley suggesting at least ~43% glacier-length loss relative to its full LGM extent. This deglaciation was accompanied by the formation of a shallow proglacial lake. Using the accumulation area ratio (AAR) method, we estimate that the ELA was lower than present by ~880 m (~1120 m a.s.l.) at 19.8 ± 0.3 ka, and ~770 m lower (~1230 m a.s.l.) at 16.7 ± 0.3 ka. Applying an estimate for temperature lapse rate, this ELA anomaly implies that local air temperature was 5 ± 1 °C colder than present (1981–2010) at 19.8 ± 0.3 ka, while it was 4.4 ± 0.9 °C colder at 16.7 ± 0.3 ka, assuming no change in precipitation. The substantial glacier retreat in response to a relatively small accompanying increases in ELA (110 m) and temperature (0.6 °C) may have been a result of the high glacier-length sensitivity of this glacier system due to its low gradient of former ice surface. Our low warming estimate differs markedly from other deglaciation studies, specifically from Rakaia River valley, which reports a much larger temperature increase at the onset of the last deglaciation. This precisely-dated moraine record along with reconstructed ELA as proxies for atmospheric conditions, provides new insight into post LGM glacier behaviour and climate conditions in New Zealand.

58 GEOSCIENCES↗

In Situ Potentiodynamic Analysis of the Electrolyte/Silicon Electrodes Interface Reactions - A Sum Frequency Generation Vibrational Spectroscopy Study

The key factor in long-term use of batteries is the formation of an electrically insulating solid layer that allows lithium ion transport but stops further electrolyte redox reactions on the electrode surface, hence solid electrolyte interphase (SEI). In this paper, we have studied a common electrolyte, 1.0 M LiPF 6 /ethylene carbonate (EC)/diethyl carbonate (DEC), reduction products on crystalline silicon (Si) electrodes in a lithium (Li) half-cell system under reaction conditions. We employed in situ sum frequency generation vibrational spectroscopy (SFG-VS) with interface sensitivity in order to probe the molecular composition of the SEI surface species under various applied potentials where electrolyte reduction is expected. We found that, with a Si(100)-hydrogen terminated wafer, a Si-ethoxy (Si-OC 2 H 5 ) surface intermediate forms due to DEC decomposition. Our results suggest that the SEI surface composition varies depending on the termination of Si surface, i.e., the acidity of the Si surface. We provide the evidence of specific chemical composition of the SEI on the anode surface under reaction conditions. This supports an electrochemical electrolyte reduction mechanism in which the reduction of the DEC molecule to an ethoxy moiety plays a key role. Finally, these findings shed new light on the formation mechanism of SEI on Si anodes in particular and on SEI formation in general.

25 ENERGY STORAGE↗

Near-terminator and earthshine photography

Photographic results obtained during the Apollo 17 flight for the near terminator and earthshine conditions are discussed. Lunar surface photographs taken in the vicinity of the sunshine terminator provide important information that is not obtained on photographs taken at higher sun evaluation angles. Earthshine photography also provides data on low relief, crater morphology, and small scale structures. Examples of photographs of the lunar surface taken under both conditions are provided.

Head, J. W.↗

Cratering motions and structural deformation in the rim of the Prairie Flat multiring explosion crater

Cratering motions and structural deformation are described for the rim of the Prairie Flat multiring crater, 85.5 m across and 5.3 m deep, which was formed by the detonation of a 500-ton TNT surface-tangent sphere. The terminal displacement and motion data are derived from marker cans and velocity gages emplaced in drill holes in a three-dimensional matrix radial to the crater. The integration of this data with a detailed geologic cross section, mapped from deep trench excavations through the rim, provides a composite view of the general sequence of motions that formed a transiently uplifted rim, overturned flap, inverted stratigraphy, downfolded rim, and deformed strata in the crater walls. Preliminary comparisons with laboratory experimental cratering and with numerical simulations indicate that explosion craters of the Prairie Flat-type generated by surface and near-surface energy sources tend to follow predictable motion sequences and produce comparable structural deformation. More specifically, central uplift and multiring impact craters with morphologies and structures comparable to Prairie Flat are inferred to have experienced similar deformational histories of the rim, such as uplift, overturning, terracing, and downfolding.

Roddy, D. J.↗