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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,747 records · Page 97
All sourcesNASA NTRSDOE OSTI
NASA NTRS1992

Charge-coupled device imaging spectroscopy of Mars. II - Results and implications for Martian ferric mineralogy

Materials similar to nanophase ferric oxides are presently seen to dominate the spectral behavior of the Martian surface in the visible-to-near-IR, in view of imaging spectroscopic observations of Mars. Attention is accordingly given to models for the formation of hematite and other ferric minerals in both current terrestrial environments and in the current and past, possibly wetter Martian climate. It is noted that imaging spectroscopy is an ideal tool for high spatial resolution spacecraft and telescopic studies of the Martian surface.

Bell, James F., III↗
DOE OSTI2023

Growth of ZrO 2 films on mesoporous silica sieve via atomic layer deposition

The atomic layer deposition of ZrO 2 thin films over the mesopores of a mesoporous silica sieve, SBA-15 (Santa Barbara Amorphous-15), using the tetrakis(dimethylamino)zirconium(IV) (TDMAZ) as ZrO 2 precursor was tested and characterized using N 2 adsorption-desorption isotherms, taking advantage of the well-defined shape and size distribution of the pores in the SBA-15. Three samples were prepared, using 2, 4, and 6 deposition cycles to control the thickness of the films. It was determined that, as the average size of the pores decreased (with the increasing number of cycles), their size distribution remained narrow, indicating a homogeneous distribution of the ZrO 2 throughout the surfaces of the SBA-15 pores. This conclusion was confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy. Further, the deposition rate appears to slow down after 4 cycles, an observation that we explain by different chemisorption properties of TDMAZ molecules over SBA-15 and ZrO 2 surface and by relating the kinetic diameter of TDMAZ with the pore diameter of SBA-15 after 4 deposition cycles: mass transport limitations have become significant at this point. They may be affected by complex factors like electronic effects caused by exposed ZrO 2 surface and the multi-directional adsorption of precursor molecules in the pore walls.

36 MATERIALS SCIENCE↗
NASA NTRS1986

Surface modification strategies for (100)3C-SiC

Several surface modificaation techniques were performed in situ in an ultrahigh vacuum as part of a program to develop electrical contacts on the (100) face of cubic SiC. The Auger electron spectroscopy line shapes and peak-to-peak heights of the Si LVV and CKLL transitions indicated changes in surface stoichiometry, bonding, and short range order. Changes in the low-energy electron diffraction pattern identified changes in the symmetry of long range ordering on the surface. Heating above 1050 C depleted the surface of Si with an activation energy of 120 kcal/mol, resulting eventually in a disordered graphitic layer which was several atomic layers thick. Bombardment by Ar ions of energies greater than 1000 eV enhanced the Si to C ratio on the surface and destroyed the LEED pattern. Long range order was recovered by simultaneous heating and ion bombardment. Finally, adsorption of Cr on the Ar ion damaged surface and subsequent desorption left a reconstructed, p(2 x 1)Si enriched surface. Similar treatments with Al did not produce a surface reconstruction.

Bellina, J. J., Jr.↗
DOE OSTI2021

In situ spectroscopic insights into the redox and acid-base properties of ceria catalysts

Cerium oxide (ceria) plays an important and fascinating role in heterogeneous catalysis as illustrated by its versatile use as a catalyst, a catalyst support, or a promotor in various oxidation and reduction reactions. Central to these reactions is the rich defect chemistry, facile redox capability, and unusual acid-base properties of ceria. Understanding the unique redox and acid-base properties of ceria is essential to build the structure-catalysis relationship so that improved catalytic functions can be achieved for ceria-based materials. Among the characterization toolbox, spectroscopic approach indisputably stands out for its unparalleled power in offering chemical insights into the surface properties of ceria at atomic and molecular level. In this review, we summarize advances in revealing the redox and acid-base properties of ceria via a variety of spectroscopic methods including optical, X-ray, neutron, electronic and nuclear spectroscopy. Both direct spectroscopy characterization and its coupling with probe molecules are analyzed to illustrate how the nature, strength and density of different surface sites are influenced by the pretreatment, the morphology and size of ceria nanoparticles. Further directions in taking advantage of in situ/operando spectroscopy for better understanding the catalysis of ceria-based materials are detailed in the summary and outlook section.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Influence of solution phase environmental heterogeneity and fluctuations on vibronic spectra: Perylene diimide molecular chromophore complexes in solution

Ensembles of ab initio parameterized Frenkel-exciton model Hamiltonians for different perylene diimide dimer systems are used, together with various dissipative quantum dynamics approaches, to study the influence of the solvation environment and fluctuations in chromophore relative orientation and packing on the vibronic spectra of two different dimer systems: a π-stacked dimer in aqueous solution in which the relative chromophore geometry is strongly confined by a phosphate bridge and a side-by-side dimer in dichloromethane involving a more flexible alkyne bridge that allows quasi-free rotation of the chromophores relative to one another. These entirely first-principles calculations are found to accurately reproduce the main features of the experimental absorption spectra, providing a detailed mechanistic understanding of how the structural fluctuations and environmental interactions influence the vibronic dynamics and spectroscopy of solutions of these multi-chromophore complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1974

MARS as viewed by Mariner 9

Photographs of the surface of the planet Mars which were obtained by the Mariner 9 space probe are presented. Areas of investigation during the Mariner 9 flight involved television coverage, ultraviolet spectroscopy, infrared spectroscopy, infrared radiometry, S-band occultation, and celestial mechanics. Descriptions of the photographs are provided to further identify the surface features and the coordinates of the area photographed are included. Emphasis is placed on the visual evidence of the effects of wind in shaping the Martian surface. Photographs of cloud formations and dust storms are analyzed.

Source record↗
DOE OSTI2023

In-situ transmission electron microscopy investigation on surface oxides thermal stability of niobium

Niobium is commonly used for superconducting quantum systems as readout resonators, capacitors, and interconnects. Structural defects at the Nb/Si and air/Nb interface may be a major source of two-level systems (TLS), which are detrimental to the device's coherence time. Thus, identifying and understanding the microscopic origin of possible TLS in Nb-based devices and their relationship to processing is key to superconducting qubit performance improvement. Here this work studied the structure and thermal stability of surface oxide on physical vapor deposited Nb films on Si wafers, using aberration-corrected (scanning) transmission electron microscopy and spectroscopy. Here, all Nb films exhibit columnar growth with strong [110] textures. After in-situ heating of the heterostructure at 360 °C inside the microscope, the initial amorphous niobium surface oxides decompose into face-centered cubic Nb nanograins in the amorphous Nb-O matrix, which may reduce microwave dissipation. Despite changes in the microstructure and chemistry of the niobium oxide surface layer due to heat treatment, the interface between the Nb and the surface oxide layer remains almost unchanged. Our comprehensive study of the Nb surface oxide decomposition mechanism may guide future superconducting qubit device optimization through interfacial scattering center and TLS minimization.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Plasmon-Mediated Intramolecular Methyl Migration with Nanoscale Spatial Control

Plasmonic materials interact strongly with light to focus and enhance electromagnetic radiation down to nanoscale volumes. Due to this localized confinement, materials that support localized surface plasmon resonances are capable of driving energetically unfavorable chemical reactions. In certain cases, the plasmonic nanostructures are able to preferentially catalyze the formation of specific photoproducts, which offers an opportunity for the development of solar-driven chemical synthesis. Here, using plasmonic environments, we report inducing an intramolecular methyl migration reaction, forming 4-methylpyridine from N-methylpyridinium. Using both experimental and computational methods, we were able to confirm the identity of the N-methylpyridinium by making spectral comparisons against possible photoproducts. This reaction involves breaking a C–N bond and forming a new C–C bond, highlighting the ability of plasmonic materials to drive complex and selective reactions. Additionally, we observe that the product yield depends strongly on optical illumination conditions. This is likely due to steric hindrance in specific regions on the nanostructured plasmonic substrate, providing an optical handle for driving plasmonic catalysis with spatial specificity. Furthermore, this work adds yet another class of reactions accessible by surface plasmon excitation to the ever-growing library of plasmon-mediated chemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Electronic Band Structures of a Germanium Halide Perovskite Semiconductor

CsGeX 3 , a class of halide perovskites, is an emergent semiconductor with ferroelectricity and potential optoelectronic properties that can be harnessed for device applications. However, measurements of the electronic structure for this class of material are still lacking. Here, in this work, we report, for the first time, the experimental band structures of CsGeI 3 , a ferroelectric halide perovskite semiconductor, through angle-resolved photoemission spectroscopy (ARPES). The crystals were cleaved along both the (110) and (111) surfaces, facilitating the observation of clear valence band dispersions in several high-symmetry momentum directions. The observed valence band is characterized by a small hole effective mass of ∼0.1m 0 at the valence band maximum, without notable spectral signatures associated with the Rashba effect. Our experimental measurements are supported by electronic structure calculations in the DFT + G0W0 framework, enabling assessment of the band orbital characteristics, dispersion, and spin-splitting. This work unveils the intrinsic electronic and transport properties of CsGeX 3 , thereby advancing the optimization of the optoelectronic properties of this class of materials.

angle-resolved photoemission spectroscopy↗
DOE OSTI2023

Correlating Tomographic Chemical Inhomogeneity and Low Energy Electronic Structure in Layered Quantum Materials

Photoemission spectroscopy (PES) is a suite of experimental tools to learn about the electronic and chemical structure of materials and surfaces. Normally implemented in a surface-sensitive manner, the research performed under this grant focused on pushing PES into less explored regimes, to reveal bulk electronic structure, to reveal tomographic (layer-resolved) chemistry and electronic structure of layered materials and heterostructures, and to reveal interface phenomena at the junction of two different materials. Standing wave (SW) spectroscopies have also been applied to PdCoO2, a material of interest due to its high conductivity and electron-hydrodynamic tendencies. This material can be modeled as an alternating layered structure consisting of metallic Pd layers and insulating CoO2 layers. Using SW XPS, the total electronic structure has been decomposed into contributions from the two layers, and computations highlighted the different many-body interactions in the two layers (Comm. Phys. 4, 143 (2021)). We have also used hard-x-ray angle-resolved photoemission spectroscopy (ARPES), to investigate LaB6, a technologically important material with widespread application as a cathode material for electron microscopes. We measured the bulk electronic structure of this material and found that the one-step model of photoemission better captured the electronic structure and correlations. This model treats the three steps of the photoemission process—excitation, transport of the photoelectron to the crystal surface, and escape into the vacuum—as a single quantum mechanically coherent process (Phys. Rev. Mater. 5, 055002 (2021)). We also applied x-ray photoelectron spectroscopy, implemented in a near total reflection grazing incidence geometry to elucidate technologically relevant interfaces, such as those between a substrate and photoresist (J. Phys. D: Appl. Phys. 54 464002 (2021)).

36 MATERIALS SCIENCE↗
DOE OSTI2020

Preliminary parameter studies to form pellets of hard materials for optical constants derived via single-angle reflectance spectroscopy

Infrared reflectance spectra can be influenced by many factors: the substrate and the thickness of the layer for liquids and the surface micromorphology, the form (powder, crystal) and the particle size for solids. All these parameters can play a role in the appearance of the measured spectrum. To avoid collecting multitudes of spectra to cover all such scenarios, the optical constants n and k, which are intrinsic properties of a material, can instead be used to model the reflectance spectrum. For solids, two techniques are often used to derive optical constants: ellipsometry and single-angle reflectance spectroscopy. For both methods, best results are usually obtained from single crystals. We have recently demonstrated for ammonium sulfate (a relatively soft material) that by optimizing certain conditions, high quality pellets with specularly reflective surfaces can be used in lieu of crystals. This was confirmed by the excellent agreement between the optical constants derived by these two methods. This work focuses on the possible extension of these methods to harder materials, starting with sodium sulfate. The first goal is to see if high quality pellet surfaces can be obtained as for ammonium sulfate. The reflectance values and the associated optical constants can also be obtained.

Diaz, Emmanuela↗
DOE OSTI2025

First in operando transient grating spectroscopy measurements on tungsten during high flux plasma operation in PISCES-RF

This work details the construction and first in operando transient grating spectroscopy measurements conducted on PISCES-RF during plasma operation. A preliminary study on a tungsten sample with varied plasma species (Ar and D 2 ), ion flux (4 × 10 21 to 6 × 10 22 ion/m 2 /s), ion energy (5 to 80 eV), and surface temperature (20 to 200 °C) is presented. Prior to plasma exposure, the thermal diffusivity and surface acoustic wave (SAW) speed, (6.9 ± 0.2) × 10 −5 m 2 /s and (2.66 ± 0.02) km/s, were measured in situ with a thermal grating period of 12.5 μm. During Ar plasma exposure, these two quantities vary according to the sample surface temperature. At low flux and varied ion energy, D 2 plasma exposure also results in thermal diffusivity and SAW speed varying with surface temperature alone. At high flux, D 2 plasma exposure results in no convincing change to the thermal diffusivity, but the SAW speed is reduced. After returning to 20 °C, post plasma exposures, the thermal diffusivity and SAW speed almost recover to the initial value prior to exposure.

Surface acoustic wave SAW↗
DOE OSTI2026

Evolution of Electronic Properties of Graphene Nanoribbons with Progressive Carving: From Straight to Porous to Chevron Ribbons

Graphene nanoribbons (GNRs) are highly versatile materials due to their unique electronic, magnetic, and optical properties, which can be precisely tuned by controlling their width, edge structure, and topology. Here, we report the on-surface synthesis and characterization of a straight N = 15 armchair GNR with periodic annulene nanopores (15-pGNR). It serves as a structural link between two well-established GNRs: the pristine N = 15 armchair GNR without pores (15-AGNR) and the chevron GNR (cGNR). With the addition of the 15-pGNR reported in this study, these three GNRs form a rare experimentally accessible series of ribbons, in which the evolution of electronic properties can be tracked upon progressive carving of a basic 15-AGNR: first, by creating periodic nanopores to form 15-pGNR and then by extending the pore area and producing meandering cGNR. We have designed a molecular precursor for the 15-pGNR and grown the nanoribbons on single-crystal gold substrates by on-surface synthesis in ultra-high vacuum (UHV) conditions. The atomically precise structure of 15-pGNR was confirmed by scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM). The band gap of 15-pGNR was studied by scanning tunneling spectroscopy (STS) and dI/dV mapping, and the occupied electronic levels were investigated by angle-resolved photoemission spectroscopy (ARPES). A theoretical and experimental comparison of 15-pGNRs, 15-AGNRs, and cGNRs demonstrates that the introduction of periodic nanopores into 15-AGNR leads to a more than 2-fold increase in its band gap. In contrast, the band gaps of 15-pGNR and cGNR differ only by about 15%. Such band gap increase can be qualitatively understood to arise from two combined effects, the periodic perforation of the graphene lattice and the confinement effect induced by the GNR width.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
NASA NTRS2008

Surface Analysis of 4-Aminothiophenol Adsorption at Polycrystalline Platinum Electrodes

Formation of self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) on polycrystalline platinum electrodes has been studied by surface analysis and electrochemistry techniques. The 4-ATP monolayer was characterized by cyclic voltammetry (CV), Raman spectroscopy, reflection absorption infrared (RAIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV) experiments give an idea about the packing quality of the monolayer. RAIR and Raman spectra for 4-ATP modified platinum electrodes showed the characteristic adsorption bands for neat 4-ATP indicating the adsorption of 4-ATP molecules on platinum surface. The adsorption on platinum was also evidenced by the presence of sulfur and nitrogen peaks by XPS survey spectra of the modified platinum electrodes. High resolution XPS studies and RAIR spectrum for platinum electrodes modified with 4-ATP indicate that molecules are sulfur-bonded to the platinum surface. The formation of S-Pt bond suggests that ATP adsorption gives up an amino terminated SAM. Thickness of the monolayer was evaluated via angle-resolved XPS (AR-XPS) analyses. Derivatization of 4-ATP SAM was performed using 16-Br hexadecanoic acid.

Rosario-Castro, Belinda I.↗
NASA NTRS2000

Evidence that the reactivity of the martian soil is due to superoxide ions

The Viking Landers were unable to detect evidence of life on Mars but, instead, found a chemically reactive soil capable of decomposing organic molecules. This reactivity was attributed to the presence of one or more as-yet-unidentified inorganic superoxides or peroxides in the martian soil. Using electron paramagnetic resonance spectroscopy, we show that superoxide radical ions (O2-) form directly on Mars-analog mineral surfaces exposed to ultraviolet radiation under a simulated martian atmosphere. These oxygen radicals can explain the reactive nature of the soil and the apparent absence of organic material at the martian surface.

long duration↗
NASA NTRS2017

Surface Monitoring of CFRP Structures for Adhesive Bonding

Adhesive bonding of composite materials requires reliable monitoring and detection of surface contaminants to assure robust and durable bonded structures. Surface treatment and effective monitoring prior to bonding is essential in order to obtain a surface free from contaminants that may degrade structural performance. Two techniques which monitor the effectiveness of the laser surface treatment of carbon fiber reinforced polymer (CFRP) materials are being investigated: laser induced breakdown spectroscopy (LIBS) and optically stimulated electron emission (OSEE). The applicability of LIBS to detect silicone contaminants on CFRP composites is studied using ~35 ns Nd:YAG laser pulses at 355 nm with a pulse energy of 45 mJ. The LIBS regime in which pulse energies are < 100 mJ is referred to as mLIBS. CFRP surfaces were contaminated with polydimethylsiloxane (PDMS), a major component of silicone based mold release agents. The presence of PDMS is found by inspecting the Si I emission line at 288.2 nm. Untreated CFRP samples and CFRP contaminated with PDMS were tested. The PDMS areal density ranged from 0.36 Â+/- 0.04 to 0.51 Â+/- 0.16 mg/cm2. The results demonstrate the successful detection of PDMS on CFRP using mLIBS. In addition, OSEE was used to measure CFRP surface cleanliness pre- and post-treatment by laser ablation on specimens contaminated with PDMS coatings from 8 nm to 1311 nm in thickness. The results showed a significant increase in the OSEE photocurrent after laser surface treatment.

Ledesma, Rodolfo↗
DOE OSTI2020

Surface Hydration and Hydroxyl Configurations of Gibbsite and Boehmite Nanoplates

Discontinuation of the bulk structure at the interface between metal oxide particles and water leads to altered bonding characteristics and unique facet-dependent molecular environments. Surface hydration and consequent hydroxylation adds further complexity to the interface, details that for metal (oxy)hydroxides are especially difficult to isolate from the background signal of bulk structural hydroxyls. Here we probe for the first time the hydroxylation and hydration structures on basal surfaces of gibbsite (?-Al(OH)3) and boehmite (?-AlOOH) nanoplates at ambient conditions, using the interface-sensitive technique vibrational sum frequency generation spectroscopy (VSFG). Hydroxyl stretching modes at the interfaces with adsorbed water layers compared directly to Raman and infrared bulk modes show that while gibbsite surface frequencies were sharp and nearly identical to those in the bulk, boehmite surface hydroxyls displayed a very different broad spectrum of states. Ab initio molecular dynamics simulations of both basal surfaces with and without hydration waters reveal that gibbsite surface hydroxyls interact only weakly with overlying hydration waters remaining essentially unperturbed, whereasthose on boehmite can interact more strongly facilitated by higher configurational degrees of freedom at the interface. The findings clearly unveil substantial differences in the hydrated interfacial dynamics of these two otherwise similar materials, with implications for their interfacial chemistry and wettability.

Sassi, Michel JPC↗