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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 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Experimental and computational studies of Criegee intermediate reactions with NH 3 and CH 3 NH 2

Ammonia and amines are emitted into the troposphere by various natural and anthropogenic sources, where they have a significant role in aerosol formation. Here, we explore the significance of their removal by reaction with Criegee intermediates, which are produced in the troposphere by ozonolysis of alkenes. Rate coefficients for the reactions of two representative Criegee intermediates, formaldehyde oxide (CH 2 OO) and acetone oxide ((CH 3 ) 2 COO) with NH 3 and CH 3 NH 2 were measured using cavity ring-down spectroscopy. Temperature-dependent rate coefficients, k(CH 2 OO + NH 3 ) = (3.1 ± 0.5) × 10 -20 T 2 exp(1011 ± 48/T) cm 3 s -1 and k(CH 2 OO + CH 3 NH 2 ) = (5 ± 2) × 10 -19 T 2 exp(1384 ± 96/T) cm 3 s -1 were obtained in the 240 to 320 K range. Both the reactions of CH 2 OO were found to be independent of pressure in the 10 to 100 Torr (N 2 ) range, and average rate coefficients k(CH 2 OO + NH 3 ) = (8.4 ± 1.2) × 10 -14 cm 3 s -1 and k(CH 2 OO + CH 3 NH 2 ) = (5.6 ± 0.4) × 10 -12 cm 3 s -1 were deduced at 293 K. An upper limit of ≤2.7 × 10 -15 cm 3 s -1 was estimated for the rate coefficient of the (CH 3 ) 2 COO + NH3 reaction. Complementary measurements were performed with mass spectrometry using synchrotron radiation photoionization giving k(CH 2 OO + CH 3 NH 2 ) = (4.3 ± 0.5) × 10-12 cm3 s-1 at 298 K and 4 Torr (He). Photoionization mass spectra indicated production of NH 2 CH 2 OOH and CH 3 N(H)CH 2 OOH functionalized organic hydroperoxide adducts from CH 2 OO + NH 3 and CH 2 OO + CH 3 NH 2 reactions, respectively. Ab initio calculations performed at the CCSD(T)(F12*)/cc-pVQZ-F12//CCSD(T)(F12*)/cc-pVDZ-F12 level of theory predicted pre-reactive complex formation, consistent with previous studies. Master equation simulations of the experimental data using the ab initio computed structures identified submerged barrier heights of -2.1 ± 0.1 kJ mol -1 and -22.4 ± 0.2 kJ mol -1 for the CH 2 OO + NH 3 and CH 2 OO + CH 3 NH 2 reactions, respectively. The reactions of NH3 and CH3NH2 with CH 2 OO are not expected to compete with its removal by reaction with (H 2 O) 2 in the troposphere. Similarly, losses of NH 3 and CH 3 NH 2 by reaction with Criegee intermediates will be insignificant compared with reactions with OH radicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Dissociation path competition of radiolysis ionization-induced molecule damage under electron beam illumination

Radiolysis ionization under electron beam illumination induces dissociation and damage of organic and biological molecules; thus, it is impossible to image the related materials by transmission electron microscopy (TEM). To understand the atomistic mechanism of radiolysis damage, we developed a systematical procedure based on real-time time-dependent density functional theory (rt-TDDFT) for simulating the radiolysis damage processes of molecules; this procedure can describe the ionization cross sections of the electronic states and the fast dissociation processes caused by hot carrier cooling and the Auger decay on deep levels. For the radiolysis damage of C 2 H 6 O 2 , our simulation unexpectedly showed that there is strong competition among three different dissociation paths, including fast dissociation caused by nonadiabatic cooling of the hot carrier; fast dissociation caused by Auger decay, which induces double ionization and Coulomb explosion; and slow dissociation caused by increased kinetic energy. As the energy of the incident electron beam changes, the time scales of these dissociation paths and their relative contributions to the molecule damage change significantly. These simulation results explain the measured mass spectra of the C 2 H 6 O 2 dissociation fragments and also provide clear competition mechanisms for blocking these dissociation paths in the TEM imaging of organic and biological materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

An Experimental and Theoretical Study of the High Temperature Reactions of the Four Butyl Radical Isomers

The high temperature gas phase chemistry of the four butyl radical isomers (n-butyl,sec-butyl, iso-butyl, andtert-butyl) was investigated in a combined experimental and theoretical study. Organic nitrites were used as convenient and clean sources of each of the butyl radical isomers. Rate coefficients for dissociation of each nitrite were obtained experimentally and are at, or close to, the high pressure limit. Low pressure experiments were performed in a diaphragmless shock tube with laser schlieren densitometry at post-shock pressures of 65, 130, and 260 Torr and post-shock temperatures of 700-1000 K. Additional experiments were conducted with iso-butyl radicals at 805 K and 8.7 bar to elucidate changes in mechanism at higher pressures. These experiments were performed in a miniature shock tube with synchrotron-based photoionization mass spectrometry. The mass spectra confirmed that scission of the O-NO bond is the primary channel by which the precursors dissociate, but they also provided evidence of a minor channel (<7.7%) through HNO loss and formation of an aldehyde. These high pressure experiments were also used to determine the disproportionation/recombination ratio for iso-butyl radicals as 0.3. Reanalysis of the lower-temperature literature and the present data yielded rate constants for the disproportionation reaction, iso-butyl + iso-butyl = iso-butene + iso-butane. A chemical kinetics model was developed for the reactions of the butyl isomers that included new paths for highly energized adducts. These adducts are formed by the addition of H, CH 3 or C 2 H 5 to the butyl radicals. Accompanying theoretical investigations show that chemically activated pathways are competitive with stabilization of the adduct by collision under the conditions of the laser schlieren experiments. These calculations also show that at 10 bar and T< 1000 K stabilization is the only important reaction, but at higher temperatures, even at 10 bar, chemically activated product channels should also be considered. Branching fractions and rate coefficients are presented for these reactions. Furthermore, this study also highlights the importance of the radical structure for determining branching ratios for disproportionation and recombination of alkyl radicals, and these were facilitated by theoretical calculations of recombination rate coefficients for the four butyl radical isomers. Overall, the results reveal previously unknown features of butyl radical chemistry under conditions that are relevant to a wide range of applications and reaction mechanisms are presented that incorporate pressure dependent rate coefficients for the key steps.

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

The electronic structure and deexcitation pathways of an isolated metalloporphyrin ion resolved by metal L-edge spectroscopy

The local electronic structure of the metal-active site and the deexcitation pathways of metalloporphyrins are crucial for numerous applications but difficult to access by commonly employed techniques. Here, we applied near-edge X-ray absorption mass spectrometry and quantum-mechanical restricted active space calculations to investigate the electronic structure of the metal-active site of the isolated cobalt(III) protoporphyrin IX cation (CoPPIX+) and its deexcitation pathways upon resonant absorption at the cobalt L-edge. The experiments were carried out in the gas phase, thus allowing for control over the chemical state and molecular environment of the metalloporphyrin. The obtained mass spectra reveal that resonant excitations of CoPPIX+ at the cobalt L3-edge lead predominantly to the formation of the intact radical dication and doubly charged fragments through losses of charged and neutral side chains from the macrocycle. The comparison between experiment and theory shows that CoPPIX + is in a 3 A 2g triplet ground state and that competing excitations to metal-centred non-bonding and antibonding σ* molecular orbitals lead to distinct deexcitation pathways.

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

Gas-phase pyrolysis of trans 3-pentenenitrile: competition between direct and isomerization-mediated dissociation

The flash pyrolysis of trans 3-pentenenitrile (3-PN, CH 3 –$CH=CH$–CH 2 –CN) was studied by combining the results of VUV photoionization mass spectra with broadband microwave spectra recorded as a function of the temperature of the pyrolysis tube. The two separated functional groups (vinyl and nitrile) open up isomerization as an initial step in competition with unimolecular dissociation. Primary products were detected by keeping the 3-PN concentration low and limiting reaction times to the traversal time of the gas in the pyrolysis tube (~100 μs). The reaction is quenched and products are cooled by expansion into vacuum before interrogation over the 8–18 GHz region using chirped-pulse broadband methods. 118 nm VUV photoionization of the same reaction mixture provides a means of detecting all products with ionization potentials below 10.5 eV with minimal fragmentation. These results are combined with a detailed computational investigation of the C 5 H 7 N and related potential energy surfaces, leading to a consistent picture of the unimolecular decomposition of 3-PN. Loss of two H-atoms to form a 79 amu product is proven from its microwave transitions to contain trans-Z-2,4-pentadienenitrile, while no pyridine is observed. Methyl loss, HCN loss, and breaking the central C(2)–C(3) bond all occur following isomerization of the position of the double bond, thereby opening up low-energy pathways to these decomposition channels.

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

Size-dependent femtosecond proton transfer in protonated methanol clusters

Methanol clusters (CH 3 OH) n are prototypical hydrogen-bonded systems that bridge isolated molecules and bulk liquid methanol. Strong-field ionization of these clusters can trigger ultrafast charge migration, proton transfer, and isomerization; however, the onset timescales of these pathways remain largely unexplored despite extensive steady-state mass-spectrometric evidence for protonation and chemical rearrangement. Here we use femtosecond time-resolved strong-field ionization and disruptive probing to directly track the early-time dynamics of methanol clusters. Transient mass spectra yield size-dependent timescales for the formation of protonated clusters H + (CH 3 OH) n (n = 1–3) and an associated CHO˙ + radical cation. We find that both proton-transfer and subsequent stabilization become markedly faster with increasing cluster size. These measurements establish methanol clusters as a complementary benchmark to water for understanding ionization-initiated proton motion and chemical reorganization in hydrogen-bonded liquids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Large-scale, nonsubtractive patterning of transparent conducting oxides by ion bombardment

While significant progress has been achieved in the fabrication and performance of transparent electronic devices, substantially less research effort has been devoted to transparent interconnects, despite their critical importance for transparent integrated circuitry. Here, we exploit the crystal disorder induced by Ar{sup +} ion bombardment to achieve efficient fabrication of electrically conductive patterns on indium oxide surfaces. The resulting ion-induced patterns are characterized by conductive atomic force microscopy, secondary ion mass spectrometry, and four-point charge transport measurements. Massively parallel patterning is demonstrated over square centimeter areas with a patterned electrical conductivity of {approx}10{sup 4} S cm{sup -1}.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Method of determination of AlGaAsSb layer composition in molecular beam epitaxy processes with regard to unintentional As incorporation

The accurate determination of the chemical composition of multicomponent antimonide layers still remains difficult. The problem becomes even more complicated when group III antimonides are grown in a MBE chamber that is also used for the growth of group III arsenides. In this paper, the composition of MBE grown AlGaAsSb layers is investigated in the context of unintentional arsenic incorporation. Control of the As concentration and a determination of the AlGaSb composition are crucial for an accurate calculation of the AlGaAsSb stoichiometry. It has been found that when using diffraction measurements with an As detection limit of 0.087%, the Al content in Al{sub 0.5}Ga{sub 0.5}Sb is determined with an accuracy of {+-}1%. Taking into account the GaSb reference from secondary ion mass spectrometry, the accuracy can be increased to {+-}0.52% of Al. The Al/Ga ratio determined for AlGaSb layers is further used for the calculation of the As content in AlGaAsSb alloys grown under the same technological conditions as the ternary layer. As a result, the procedure for the accurate determination of stoichiometry coefficients in this material is recommended.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Ion-beam mixing in crystalline and amorphous germanium isotope multilayers

Gallium (Ga) implantation induced self-atom mixing in crystalline and amorphous germanium (Ge) is investigated utilizing isotopically controlled Ge multilayer structures grown by molecular beam epitaxy. The distribution of the Ga ions and the ion-beam induced depth-dependent mixing of the isotope structure was determined by means of secondary ion mass spectrometry. Whereas the distribution of Ga in the crystalline and amorphous Ge is very similar and accurately reproduced by computer simulations based on binary collision approximation (BCA), the ion-beam induced self-atom mixing is found to depend strongly on the state of the Ge structure. The experiments reveal stronger self-atom mixing in crystalline than in amorphous Ge. Atomistic simulations based on BCA reproduce the experimental results only when unphysically low Ge displacement energies are assumed. Analysis of the self-atom mixing induced by silicon implantation confirms the low displacement energy deduced within the BCA approach. This demonstrates that thermal spike mixing contributes significantly to the overall mixing of the Ge isotope structures. The disparity observed in the ion-beam mixing efficiency of crystalline and amorphous Ge indicates different dominant mixing mechanisms. We propose that self-atom mixing in crystalline Ge is mainly controlled by radiation enhanced diffusion during the early stage of mixing before the crystalline structure turns amorphous, whereas in an already amorphous state self-atom mixing is mediated by cooperative diffusion events.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Determination of secondary ion mass spectrometry relative sensitivity factors for polar and non-polar ZnO

Zinc oxide (ZnO) is regarded as a promising material for optoelectronic devices, due to its electronic properties. Solely, the difficulty in obtaining p-type ZnO impedes further progress. In this connection, the identification and quantification of impurities is a major demand. For quantitative information using secondary ion mass spectrometry (SIMS), so-called relative sensitivity factors (RSF) are mandatory. Such conversion factors did not yet exist for ZnO. In this work, we present the determined RSF values for ZnO using primary (ion implanted) as well as secondary (bulk doped) standards. These RSFs have been applied to commercially available ZnO substrates of different surface termination (a-plane, Zn-face, and O-face) to quantify the contained impurities. Although these ZnO substrates originate from the same single-crystal, we observe discrepancies in the impurity concentrations. These results cannot be attributed to surface termination dependent RSF values for ZnO.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Contactless monitoring of Ge content and B concentration in ultrathin single and double layer Si{sub 1-x}Ge{sub x} epitaxial films using multiwavelength micro-Raman spectroscopy

Non-contact monitoring of Ge content and B concentration in single and double Si{sub 1-x}Ge{sub x} epitaxial layers on Si(100) device wafers was attempted using high-resolution, multiwavelength micro-Raman spectroscopy. The Ge content and B concentration determined by secondary ion mass spectroscopy (SIMS) depth profiling showed very strong correlation with the position and full-width-at-half-maximum of the Si-Si peak from the Si{sub 1-x}Ge{sub x} epitaxial layers as determined by Raman measurements. High resolution X-ray diffraction (HRXRD) characterization was done for all wafers to determine Ge and B sensitivity and form comparisons with Raman and SIMS analysis. The non-destructive, in-line monitoring of Ge content and B concentration of single and double Si{sub 1-x}Ge{sub x} epitaxial layers with thickness ranging from 5 {approx} 120 nm, on small area monitoring pads, was successfully demonstrated by multiwavelength micro-Raman spectroscopy during epitaxial process optimization, material property verification, and quality control applications.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Deep traps in nonpolar m-plane GaN grown by ammonia-based molecular beam epitaxy

Deep level defects in nonpolar m-plane GaN grown by ammonia-based molecular beam epitaxy were characterized using deep level transient spectroscopy (DLTS) and deep level optical spectroscopy (DLOS) and compared with polar c-plane GaN that was grown simultaneously in the same growth run. Significant differences in both the levels present and their concentrations were observed upon comparison of both growth orientations. DLTS revealed electron traps with activation energies of 0.14 eV, 0.20 eV, and 0.66 eV in the m-plane material, with concentrations that were {approx}10-50 x higher than traps of similar activation energies in the c-plane material. Likewise, DLOS measurements showed {approx}20 x higher concentrations of both a C{sub N} acceptor-like state at E{sub C} - 3.26 eV, which correlates with a high background carbon concentration observed by secondary ion mass spectroscopy for the m-plane material [A. Armstrong, A. R. Arehart, B. Moran, S. P. DenBaars, U. K. Mishra, J. S. Speck, and S. A. Ringel, Appl. Phys. Lett. 84, 374 (2004)], and the V{sub Ga}-related state level at E{sub C} - 2.49 eV, which is consistent with an enhanced yellow luminescence observed by photoluminescence. The findings suggest a strong impact of growth dynamics on the incorporation of impurities and electrically active native point defects as a function of GaN growth plane polarity.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Tunneling current modulation by Ge incorporation into Si oxide films for flash memory applications

Current-voltage characteristic for a Ge-incorporated Si oxide was investigated. Current enhancement was observed for the electric field larger than 10 MV/cm. Such a current enhancement only under high electric field is expected to improve programming performance without deteriorating reading performance. From secondary ion mass spectrometry and hard x-ray photoelectron spectroscopy analyses and current simulation, it is concluded that the Ge impurity in Ge{sup 4+} state around the tunnel oxide/substrate interface enhances the current by trap-assisted tunneling. The programming current enhancement induced by the Ge incorporation is expected to be one of the promising solutions for the next-generation flash memory.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Oxygen cluster anions revisited: Solvent-mediated dissociation of the core O{sub 4}{sup -} anion

The electronic structure and photochemistry of the O{sub 2n}{sup -}(H{sub 2}O){sub m}, n= 1-6, m= 0-1 cluster anions is investigated at 532 nm using photoelectron imaging and photofragment mass-spectroscopy. The results indicate that both pure oxygen clusters and their hydrated counterparts with n{>=} 2 form an O{sub 4}{sup -} core. Fragmentation of these clusters yields predominantly O{sub 2}{sup -} and O{sub 2}{sup -}{center_dot}H{sub 2}O anionic products, with the addition of O{sub 4}{sup -} fragments for larger parent clusters. The fragment autodetachment patterns observed for O{sub 6}{sup -} and larger O{sub 2n}{sup -} species, as well as some of their hydrated counterparts, indicate that the corresponding O{sub 2}{sup -} fragments are formed in excited vibrational states (v {>=} 4). Yet, surprisingly, the unsolvated O{sub 4}{sup -} anion itself does not show fragment autodetachment at 532 nm. It is hypothesized that the vibrationally excited O{sub 2}{sup -} is formed in the intra-cluster photodissociation of the O{sub 4}{sup -} core anion via a charge-hopping electronic relaxation mechanism mediated by asymmetric solvation of the nascent photofragments: O{sub 4}{sup -}{yields} O{sub 2}{sup -}(X{sup 2}{Pi}{sub g}) + O{sub 2}(a{sup 1}{Delta}{sub g}) {yields} O{sub 2}(X{sup 3}{Sigma}{sub g}{sup -}) + O{sub 2}{sup -}(X{sup 2}{Pi}{sub g}). This process depends on the presence of solvent molecules and leads to vibrationally excited O{sub 2}{sup -}(X{sup 2}{Pi}{sub g}) products.

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

Component analysis of a mixed beam generated by vacuum electrospray of an ionic liquid

Vacuum electrospray of a quaternary ammonium ionic liquid, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl) amide (DEME-TFSA), was investigated to develop a primary ion source for secondary ion mass spectrometry (SIMS). Since the ionic liquid contains many methyl and ethyl groups as well as protons, its beam is expected to efficiently produce protonated molecules for SIMS analysis of organic materials. Experimental results showed that the beam consisted of charged particles of m/z about 1000 and charged droplets of m/z > 10{sup 5}. The current components of both the charged particles and droplets changed with the applied voltage and the flow rate of the ionic liquid. With decreasing flow rate, the current component of the charged droplets increased, whereas that of the charged particles decreased. The m/z values of the charged droplets diminished with decreasing flow rate and increasing capillary voltage. In addition to masses and charge numbers, the numbers of the charged droplets and the charged particles were estimated.

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

Absolute photoionization cross-section of the propargyl radical

Using synchrotron-generated vacuum-ultraviolet radiation and multiplexed time-resolved photoionization mass spectrometry we have measured the absolute photoionization cross-section for the propargyl (C{sub 3}H{sub 3}) radical, {sigma}{sub propargyl}{sup ion}(E), relative to the known absolute cross-section of the methyl (CH{sub 3}) radical. We generated a stoichiometric 1:1 ratio of C{sub 3}H{sub 3} : CH{sub 3} from 193 nm photolysis of two different C{sub 4}H{sub 6} isomers (1-butyne and 1,3-butadiene). Photolysis of 1-butyne yielded values of {sigma}{sub propargyl}{sup ion}(10.213 eV)=(26.1{+-}4.2) Mb and {sigma}{sub propargyl}{sup ion}(10.413 eV)=(23.4{+-}3.2) Mb, whereas photolysis of 1,3-butadiene yielded values of {sigma}{sub propargyl}{sup ion}(10.213 eV)=(23.6{+-}3.6) Mb and {sigma}{sub propargyl}{sup ion}(10.413 eV)=(25.1{+-}3.5) Mb. These measurements place our relative photoionization cross-section spectrum for propargyl on an absolute scale between 8.6 and 10.5 eV. The cross-section derived from our results is approximately a factor of three larger than previous determinations.

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

Studying femtosecond-laser hyperdoping by controlling surface morphology

We study the fundamental properties of femtosecond-laser (fs-laser) hyperdoping by developing techniques to control the surface morphology following laser irradiation. By decoupling the formation of surface roughness from the doping process, we study the structural and electronic properties of fs-laser doped silicon. These experiments are a necessary step toward developing predictive models of the doping process. We use a single fs-laser pulse to dope silicon with sulfur, enabling quantitative secondary ion mass spectrometry, transmission electron microscopy, and Hall effect measurements. These measurements indicate that at laser fluences at or above 4 kJ m{sup -2}, a single laser pulse yields a sulfur dose >(3 {+-} 1) x 10{sup 13} cm{sup -2} and results in a 45-nm thick amorphous surface layer. Based on these results, we demonstrate a method for hyperdoping large areas of silicon without producing the surface roughness.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Oxygen incorporation in homoepitaxial N-polar GaN grown by radio frequency-plasma assisted molecular beam epitaxy: Mitigation and modeling

We have investigated the effect of gallium deposition and desorption cycles and ultrathin (15 A) AlN layers on the oxygen impurity concentrations in homoepitaxial N-polar GaN layers. Secondary ion mass spectroscopy (SIMS) indicates that three Ga deposition and desorption cycles reduce the total oxygen by 70%-80%, while ten cycles reduces the total oxygen by more than 90%. We present a model of surface segregation and incorporation which accurately captures the distribution of oxygen in these layers. By fitting the model to the SIMS data, we are able to determine the fraction of an oxygen layer adsorbed on a GaN surface which segregates upon initiation of epitaxial GaN growth. Under the conditions investigated, we find this fraction to be 80%.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗