Search NASA⌕ Search

SEARCH · Search NASA

Results for “Capping”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,675 records · Page 93
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Nanocatalyst shape and composition during nucleation of single-walled carbon nanotubes

The dynamic evolution of nanocatalyst particle shape and carbon composition during the initial stages of single-walled carbon nanotube growth by chemical vapor deposition synthesis is investigated. Classical reactive and ab initio molecular dynamics simulations are used, along with environmental transmission electron microscope video imaging analyses. A clear migration of carbon is detected from the nanocatalyst/substrate interface, leading to a carbon gradient showing enrichment of the nanocatalyst layers in the immediate vicinity of the contact layer. However, as the metal nanocatalyst particle becomes saturated with carbon, a dynamic equilibrium is established, with carbon precipitating on the surface and nucleating a carbon cap that is the precursor of nanotube growth. A carbon composition profile decreasing towards the nanoparticle top is clearly revealed by the computational and experimental results that show a negligible amount of carbon in the nanoparticle region in contact with the nucleating cap. The carbon composition profile inside the nanoparticle is accompanied by a well-defined shape evolution of the nanocatalyst driven by the various opposing forces acting upon it both from the substrate and from the nascent carbon nanostructure. In conclusion, this new understanding suggests that tuning the nanoparticle/substrate interaction would provide unique ways of controlling the nanotube synthesis.

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

Control of clustering behavior in anionic cerium( III ) corrole complexes: from oligomers to monomers

Here, the first synthesis of anion capped cerium corrole complexes is reported. Unusual clustering of the lanthanide corrole units has been found and the degree of aggregation can be controlled by the choice of the capping ligand. A polymeric structure 1a, with the general formula [Cor–Ce(THF)–Cp–Na] n (Cor = 5,15-bis(2,4,6-trimethylphenyl)-10-(4 methoxyphenyl)-corrole, THF = tetrahydrofuran), is formed using sodium cyclopentadienide (NaCp) and a dimeric structure 2a, with the general formula [Cor–Ce–Tp] 2 , is formed when potassium tris(pyrazolyl)borate (KTp) is used. Encapsulation of the counter-cation leads to the isolation of the monomeric structures 1b and 2b, with the general formulas [AM(2.2.2-cryptand)][Cor–Cp–X] (AM = Na or K, X = Cp or Tp). The structural and spectroscopic properties of the complexes have been investigated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

The remarkable influence of N , O -ligands in the assembly of a bis-calix[4]arene-supported [Mn IV 2 Mn III 10 Mn II 8 ] cluster

We report that calix[4]arenes are versatile ligands, capable of supporting the formation of a wide variety of polymetallic clusters comprising 3 d , 4 f or 3 d -4 f metal ions. Calixarene-based metal ion fragments act as both bridging and structure capping moieties in these systems, and this behaviour is systematically extended upon moving to bis-calix[4]arene, a relatively new ligand in which two calix[4]arenes are tethered at the methylene bridge position. N,O -Ligands greatly influence cluster formation with bis-calix[4]arene, affording a remarkable mixed-valence [Mn IV 2 Mn III 10 Mn II 8 ] cluster that displays coordination chemistry typical of each ligand type, but also new structure capping behaviour for the latter.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Root-growth of boron nitride nanotubes: experiments and ab initio simulations

We have synthesized boron nitride nanotubes (BNNTs) in an arc in presence of boron and nitrogen species. We find that BNNTs are often attached to large nanoparticles, suggesting that root-growth is a likely mechanism for their formation. Moreover, the tube-end nanoparticles are composed of boron, without transition metals, indicating that transition metals are not necessary for the arc synthesis of BNNTs. To gain further insight into this process we have studied key mechanisms for root growth of BNNTs on the surface of a liquid boron droplet by ab initio molecular dynamics simulations. We find that nitrogen atoms reside predominantly on the droplet surface where they organize to form boron nitride islands below 2400 K. To minimize contact with the liquid particle underneath, the islands assume non-planar configurations that are likely precursors for the thermal nucleation of cap structures. Once formed, the caps are stable and can easily incorporate nitrogen and boron atoms at their base, resulting in further growth. Our simulations support the root-growth mechanism of BNNTs and provide comprehensive evidence of the active role played by liquid boron.

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

Ligand dynamics control structure, elasticity, and high-pressure behavior of nanoparticle superlattices

Precise engineering of nanoparticle superlattices (NPSLs) for energy applications requires a molecular-level understanding of the physical factors governing their morphology, periodicity, mechanics, and response to external stimuli. Such knowledge, particularly the impact of ligand dynamics on physical behavior of NPSLs, is still in its infancy. Here in this paper, we combine coarse-grained molecular dynamics simulations, and small angle X-ray scattering experiments in a diamond anvil cell to demonstrate that coverage density of capping ligands (i.e., number of ligands per unit area of a nanoparticle's surface), strongly influences the structure, elasticity, and high-pressure behavior of NPSLs using face-centered cubic PbS-NPSLs as a representative example. We demonstrate that ligand coverage density dictates (a) the extent of diffusion of ligands over NP surfaces, (b) spatial distribution of the ligands in the interstitial spaces between neighboring NPs, and (c) the fraction of ligands that interdigitate across different nanoparticles. We find that below a critical coverage density (1.8 nm-2 for 7 nm PbS NPs capped with oleic acid), NPSLs collapse to form disordered aggregates via sintering, even under ambient conditions. Above the threshold ligand coverage density, NPSLs surprisingly preserve their crystalline order even under high applied pressures (~40–55 GPa), and show a completely reversible pressure behavior. This opens the possibility of reversibly manipulating lattice spacing of NPSLs, and in turn, finely tuning their collective electronic, optical, thermo-mechanical, and magnetic properties.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2021

Cyclic strain enhances the early stage mineral nucleation and the modulus of demineralized bone matrix

The adaptive response of bones to mechanical loading is essential for musculoskeletal development. Despite the importance of collagen in bone mineralization, little is known about how cyclic strain influences physicochemical responses of collagen, especially at the early stage of mineralization when the levels of strain are higher than those in mature bones. The findings in this study show that, without any cell-mediated activity, cyclic strain increases nucleation rates of calcium phosphate (CaP) nanocrystals in highly-organized collagen matrices. The cyclic strain enhances the transport of mineralization fluids with nucleation precursors into the matrix, thus forming more CaP nanocrystals and increasing the elastic modulus of the collagen matrix. The results also suggest that the multiscale spatial distribution of nanocrystals in the fibrous collagen network determines tissue-level mechanical properties more critically than the total mineral content. Furthermore, by linking nano- and micro-scale observations with tissue-level mechanical properties, we provide new insights into designing better biomaterials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Electronically-coupled redox centers in trimetallic cobalt complexes

Synthesis and isolation of molecular building blocks of metal–organic frameworks (MOFs) can provide unique opportunities for characterization that would otherwise be inaccessible due to the heterogeneous nature of MOFs. Herein, we report a series of trinuclear cobalt complexes incorporating dithiolene ligands, triphenylene-2,3,6,7,10,11-hexathiolate (THT) (1 3+ ), and benzene hexathiolate (BHT) (2 3+ ), with 1,1,1,-tris(diphenylphosphinomethyl)ethane (triphos) employed as the capping ligand. Single crystal X-ray analyses of 1 3+ and 2 3+ display three five-coordinate cobalt centers bound to the triphos and dithiolene ligands in a distorted square pyramidal geometry. Cyclic voltammetry studies of 1 3+ and 2 3+ reveal three redox features associated with the formation of mixed valence states due to the sequential reduction of the redox-active metal centers (Co III/II ). Using this electrochemical data, the comproportionality values were determined for 1 and 2 (log K c = 1.4 and 1.5 for 1, and 4.7 and 5.8 for 2), suggesting strong resonance-stabilized coupling of the metal centers, with stronger electronic coupling observed for complex 2 compared to that for complex 1. Cyclic voltammetry studies were also performed in solvents of varying polarity, whereupon the difference in the standard potentials (ΔE 1/2 ) for 1 and 2 was found to shift as a function of the polarity of the solvent, indicating a negative correlation between the dielectric constant of the electrochemical medium and the stability of the mixed valence species. Spectroelectrochemical studies of in situ generated multi-valent (MV) states of complexes 1 and 2 display characteristic NIR intervalence charge transfer (IVCT) bands, and analysis of the IVCT transitions for complex 2 suggests a weakly coupled class II multi-valent species and relatively large electronic coupling factors (1700 cm –1 for the first multi-valent state of 2 2+ , and 1400 and 4000 cm –1 for the second multi-valent state of 2 + ). Here, density functional theory (DFT) calculations indicate a significant deviation in relative energies of the frontier orbitals of complexes 1 3+ , 2 3+ , and 3 + that contrasts those calculated for the analogous trinuclear cobalt dithiolene complexes employing pentamethylcyclopentadienyl (Cp*) as the capping ligand (Co 3 Cp* 3 THT and Co 3 Cp* 3 BHT, respectively), and may be a result of the cationic nature of complexes 1 3+ , 2 3+ , and 3 + .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

A bis-calix[4]arene-supported [Cu II 16 ] cage

Reaction of 2,2'-bis-p- t Bu-calix[4]arene (H 8 L) with Cu(NO 3 ) 2 ·3H 2 O and N-methyldiethanolamine (Me-deaH 2 ) in a basic dmf/MeOH mixture affords [Cu II 16 (L) 2 (Me-dea) 4 (μ 4 -NO 3 ) 2 (μ-OH) 4 (dmf) 3.5 (MeOH) 0.5 (H 2 O) 2 ](H 6 L)·16dmf·4H 2 O (4), following slow evaporation of the mother liquor. The central core of the metallic skeleton describes a tetracapped square prism, [Cu 12 ], in which the four capping metal ions are the CuII ions housed in the calix[4]arene polyphenolic pockets. The [Cu II 8 ] square prism is held together “internally” by a combination of hydroxide and nitrate anions, with the N-methyldiethanolamine co-ligands forming dimeric [Cu II 2 ] units which edge-cap above and below the upper and lower square faces of the prism. Charge balance is maintained through the presence of one doubly deprotonated H 6 L 2- ligand per [Cu 16 ] cluster. Magnetic susceptibility measurements reveal the predominance of strong antiferromagnetic exchange interactions and an S = 1 ground state, while EPR is consistent with a large zero-field splitting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Scalable and adaptable two-ligand co-solvent transfer methodology for gold bipyramids to organic solvents

Large and faceted nanoparticles, such as gold bipyramids, presently require synthesis using alkyl ammonium halide ligands in aqueous conditions to stabilize the structure, which impedes subsequent transfer and suspension of such nanoparticles in low polarity solvents despite success with few nanometer gold nanoparticles of shapes such as spheres. Phase transfer methodologies present a feasible avenue to maintain colloidal stability of suspensions and move high surface energy particles into organic solvent environments. Here, we present a method to yield stable suspensions of gold bipyramids in low-polarity solvents, including methanol, dimethylformamide, chloroform, and toluene, through the requisite combination of two capping agents and the presence of a co-solvent. By utilizing PEG-SH functionalization for stability, dodecanethiol (DDT) as the organic-soluble capping agent, and methanol to aid in the phase transfer, gold bipyramids with a wide-range of aspect ratios and sizes can be transferred between water and chloroform readily and maintain colloidal stability. Subsequent transfer to various organic and low-polarity solvents is then demonstrated for the first time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Enhanced upconversion and photoconductive nanocomposites of lanthanide-doped nanoparticles functionalized with low-vibrational-energy inorganic ligands

Upconverting nanoparticles (UCNPs) convert near-infrared (IR) light into higher-energy visible light, allowing them to be used in applications such as biological imaging, nano-thermometry, and photodetection. It is well known that the upconversion luminescent efficiency of UCNPs can be enhanced by using a host material with low phonon energies, but the use of low-vibrational-energy inorganic ligands and non-epitaxial shells has been relatively underexplored. Here, we investigate the functionalization of lanthanide-doped NaYF4 UCNPs with low-vibrational-energy Sn2S64- ligands. Raman spectroscopy and elemental mapping are employed to confirm the binding of Sn2S64- ligands to UCNPs. This binding enhances upconversion efficiencies up to a factor of 16, consistent with an increase in the luminescent lifetimes of the lanthanide ions. Annealing Sn2S64--capped UCNPs results in the formation of a nanocomposite comprised of UCNPs embedded within an interconnected matrix of SnS2, enabling each UCNP to be electrically accessible through the semiconducting SnS2 matrix. This facilitates the integration of UCNPs into electronic devices, which we demonstrate through the fabrication of a UCNP-SnS2 photodetector that detects UV and near-IR light. Our findings show the promise of using inorganic capping agents to enhance the properties of UCNPs while facilitating their integration into optoelectronic devices.

Pan, Jia-Ahn↗
DOE OSTI2013

Wet chemical synthesis and characterization of AgGaSe{sub 2} nanoparticles

AgGaSe{sub 2} compound semiconductor nanoparticles were synthesized by wet chemical method using mercaptoacetic acid as a capping agent at room temperature. The synthesized powders belong to chalcopyrite structure confirmed by powder XRD. The surface morphology and crystalline size were observed by high resolution scanning electron microscope (HR-SEM). The stoichiometric composition of AgGaSe{sub 2} nanoparticles was confirmed by Energy dispersive X-ray (EDX) analysis. Different functional group vibrations of mercaptoacetic acid capped nanoparticles were studied using FT-IR spectrum. The absorbance and optical bandgap of the nanoparticles were determined using diffuse reflectance spectroscopy (DRS).

36 MATERIALS SCIENCE↗
DOE OSTI2013

Structural enhancement of ZnO on SiO{sub 2} for photonic applications

Multi-layer thin films are often the basis of photonic devices. Zinc oxide (ZnO) with its excellent optoelectronic properties can serve as a high quality emitter in structures like microdisks or photonic crystals. Here, we present a detailed study on the enhancement of the structural properties of low-temperature MBE grown ZnO on silica (SiO{sub 2}). By thermal annealing a grain coalescence of the initially polycrystalline layer leads to an enhancement of the electronic structure, indicated by a blue shift of the photoluminescence (PL) signal maximum. Oxygen atmosphere during the annealing process prevents the creation of intrinsic defects by out-diffusion. Pre-annealing deposited SiO{sub 2} capping layers instead obstruct the recrystallization and lead to less intense emission. While thin capping layers partially detach from the ZnO film at high temperatures and cause higher surface roughness and the weakest emission, thicker layers remain smoother and exhibit a significantly stronger photoluminescence.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Adjustment of threshold voltage in AlN/AlGaN/GaN high-electron mobility transistors by plasma oxidation and Al{sub 2}O{sub 3} atomic layer deposition overgrowth

We discuss possibilities of adjustment of a threshold voltage V{sub T} in normally off GaN high-electron mobility transistors (HEMTs) without compromising a maximal drain current I{sub DSmax}. Techniques of a low power plasma or thermal oxidation of 2-nm thick AlN cap over 3-nm thick AlGaN barrier are developed and calibrated for a thorough oxidation of the cap with a minimal density of surface donors at the inherent oxide-semiconductor interface. It has been shown that while a thermal oxidation technique leads to the channel and/or interface degradation, low density of surface donors and scalability of V{sub T} with additionally overgrown Al{sub 2}O{sub 3} may be obtained for plasma oxidized HEMTs. With 10-nm thick Al{sub 2}O{sub 3} deposited at 100 °C by atomic-layer deposition, we obtained V{sub T} of 1.6 V and I{sub DSmax} of 0.48 A/mm at a gate voltage of V{sub GS} = 8 V. Density of surface donors was estimated to be about 1.2 × 10{sup 13} cm{sup −2}, leaving most of the negative polarization charge at the semiconductor surface uncompensated. Further reduction of surface donors may be needed for even higher V{sub T}.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Influence of the interface on the magnetic properties of ferromagnetic ultrathin films with various adjacent copper thicknesses

The interface and magnetic properties of two series of films with Ta(5 nm)/Fe{sub 20}Ni{sub 80}Nd{sub 0.017}(3 nm)/Cu(t nm) and Ta(5 nm)/Cu(t nm)/Fe{sub 50}Co{sub 50}Gd{sub 0.07}(3 nm)/Cu(2 nm) structures have been investigated by atomic force microscopy, vibrating sample magnetometer, and ferromagnetic resonance (FMR). The roughness of all films increases with increasing copper thickness, which causes the different grain sizes in the surface of films. The coercivity of FeCo-Gd films increases with increasing thickness of inserted Cu layer while decreases with increasing thickness of Cu capping layer for FeNi-Nd films. FMR linewidth exhibits huge dependence on the thickness of inserted Cu layer for FeCo-Gd films, increasing from 2270 to 3680 Oe, which comes from the additional contribution of effect of the two-magnon scattering. And the thickness of Cu capping layer shows also an influence on FMR linewidth of FeNi-Nd films, increasing from 190 to 320 Oe, which mainly comes from intrinsic FMR linewidth and plus minor inhomogeneous broadening. All of these extrinsic linewidth broadening are related to the interface roughness.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Fixed interface charges between AlGaN barrier and gate stack composed of in situ grown SiN and Al{sub 2}O{sub 3} in AlGaN/GaN high electron mobility transistors with normally off capability

Using a generalized extraction method, the fixed charge density N{sub int} at the interface between in situ deposited SiN and 5 nm thick AlGaN barrier is evaluated by measurements of threshold voltage V{sub th} of an AlGaN/GaN metal insulator semiconductor high electron mobility transistor as a function of SiN thickness. The thickness of the originally deposited 50 nm thick SiN layer is reduced by dry etching. The extracted N{sub int} is in the order of the AlGaN polarization charge density. The total removal of the in situ SiN cap leads to a complete depletion of the channel region resulting in V{sub th} = +1 V. Fabrication of a gate stack with Al{sub 2}O{sub 3} as a second cap layer, deposited on top of the in situ SiN, is not introducing additional fixed charges at the SiN/Al{sub 2}O{sub 3} interface.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Three-terminal magnetic tunneling junction device with perpendicular anisotropy CoFeB sensing layer

We demonstrated read and write characteristics of a three terminal memory device with a perpendicular anisotropy-free layer of a strip of [Co/Ni] and a low-switching perpendicular-anisotropy CoFeB/MgO sensing layer. This new design of the cell results in a small cell area. The switching magnetic field of the sensing layer can be decreased by changing sputtering gas for the Ta-cap from Ar to Kr. An electron energy-loss spectroscopy analysis of the cross-section of the magnetic tunneling junction (MTJ) revealed that the boron content in CoFeB with a Kr-sputtered Ta-cap was smaller than that with an Ar-sputtered one. A change in resistance for the MTJ was observed that corresponded to the magnetic switching of the Co/Ni wire and its magnetoresistance ratio and critical current were 90% and 0.8 mA, respectively.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Cleaning of optical surfaces by capacitively coupled RF discharge plasma

In this paper, we report cleaning of carbon capped molybdenum (Mo) thin film by in-house developed radio frequency (RF) plasma reactor, at different powers and exposure time. Carbon capped Mo films were exposed to oxygen plasma for different durations at three different power settings, at a constant pressure. After each exposure, the thickness of the carbon layer and the roughness of the film were determined by hard x-ray reflectivity measurements. It was observed that most of the carbon film got removed in first 15 minutes exposure. A high density layer formed on top of the Mo film was also observed and it was noted that this layer cannot be removed by successive exposures at different powers. A significant improvement in interface roughness with a slight improvement in top film roughness was observed. The surface roughness of the exposed and unexposed samples was also confirmed by atomic force microscopy measurements.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗