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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 73 records · Page 4

On the Counter‐intuitive Heterogeneous Electron Transfer Barrier Properties of Alkanethiolate Monolayers on Gold: Smooth versus Rough Surfaces

Abstract Alkanethiolate monolayers formed on rough gold surfaces can, somewhat surprisingly, act as stronger barriers to heterogeneous electron transfer than those on smooth gold surfaces. This paper presents a possible explanation for this observation by constructing simple geometric models of a “rough” and “smooth” gold surface to examine how microscopic roughness differences can affect the nucleation/growth of the adlayer and size/density of structural defects. Expectedly, the number of defects predicted for adlayers formed on smooth gold is lower than any of those for rough gold. The counter‐intuitive result is that the sizes of a small portion of the defects in the adlayer on the smooth surface are larger than any of those found on the rough surface. The potential implications of these results are discussed.

Chemistry↗

Minimizing Crinkling of Soft Specimens Using Holey Gold Films on Molybdenum Grids for Cryogenic Electron Microscopy

We introduce a novel composite holey gold support that prevents cryo-crinkling and reduces beam-induced motion of soft specimens, building on the previously introduced all-gold support. The composite holey gold support for high-resolution cryogenic electron microscopy of soft crystalline membranes was fabricated in two steps. In the first step, a holey gold film was transferred on top of a molybdenum grid. In the second step, a continuous thin carbon film was transferred onto the holey gold film. This support (Au/Mo grid) was used to image crystalline synthetic polymer membranes. The low thermal expansion of Mo is not only expected to avoid cryo-crinkling of the membrane when the grids are cooled to cryogenic temperatures, but it may also act to reduce whatever crinkling existed even before cooling. Here, the Au/Mo grid exhibits excellent performance with specimens tilted to 45°. This is demonstrated by quantifying beam-induced motion and differences in local defocus values. In addition, images of specimens on the Au/Mo grids that are tilted at 45° show high-resolution information of the crystalline membranes that, after lattice-unbending, extends beyond 1.5 Å in the direction perpendicular to the tilt axis.

36 MATERIALS SCIENCE↗

Light Exposure Promotes Degradation of Intermediates and Growth of Phosphine-Ligated Gold Clusters

Subnanometer clusters exhibit unique properties not observed at the bulk or nanometer scale. Many applications, however, require clusters to be monodisperse in size and composition.While substantial progress has been made empirically on producing specific-sized gold clusters using different ligands, the mechanisms of cluster formation remain insufficiently understood. Using high mass-resolution electrospray ionization mass spectrometry (ESI-MS), we characterized the formation of cationic triphenylphosphine-ligated gold clusters [Aux(PPh3)y z+] in solution. Our data provides evidence that small hydrogen-containing intermediate “building blocks” (i.e., Au2(PPh3)2H+, Au4(PPh3)4H+, and Au7(PPh3)7H5 2+) are responsible for the growth of larger gold clusters (i.e., Au6(PPh3)6 2+ and Au8(PPh3)7 2+) over several hours. In addition, intermediate degradation and cluster growth are shown to be dependent on irradiation of the reacting solution with light. Specifically, the rate of growth of large clusters is demonstrated to scale with the intensity of light exposure. Complementary theoretical calculations were also performed that provide molecular-level insight into the nature of the bonding between the hydrogens and gold atoms in the intermediate Au-phosphine clusters. Collectively, our joint experimental and theoretical findings advance the understanding of the factors at play in the size-selective synthesis of ligated gold clusters in solution.

Hewitt, Michael A.↗

Heterophase fcc-2H-fcc gold nanorods

The crystal phase-based heterostructures of noble metal nanomaterials are of great research interest for various applications, such as plasmonics and catalysis. However, the synthesis of unusual crystal phases of noble metals still remains a great challenge, making the construction of heterophase noble metal nanostructures difficult. Here, we report a one-pot wet-chemical synthesis of well-defined heterophase fcc-2H-fcc gold nanorods (fcc: face-centred cubic; 2H: hexagonal close-packed with stacking sequence of "AB") at mild conditions. Single particle-level experiments and theoretical investigations reveal that the heterophase gold nanorods demonstrate a distinct optical property compared to that of the conventional fcc gold nanorods. Moreover, the heterophase gold nanorods possess superior electrocatalytic activity for the carbon dioxide reduction reaction over their fcc counterparts under ambient conditions. First-principles calculations suggest that the boosted catalytic performance stems from the energetically favourable adsorption of reaction intermediates, endowed by the unique heterophase characteristic of gold nanorods.

36 MATERIALS SCIENCE↗

Inverse metal-assisted chemical etching of germanium with gold and hydrogen peroxide

Abstract Metal-assisted chemical etching (MACE) is a flexible technique for texturing the surface of semiconductors. In this work, we study the spatial variation of the etch profile, the effect of angular orientation relative to the crystallographic planes, and the effect of doping type. We employ gold in direct contact with germanium as the metal catalyst, and dilute hydrogen peroxide solution as the chemical etchant. With this catalyst-etchant combination, we observe inverse-MACE, where the area directly under gold is not etched, but the neighboring, exposed germanium experiences enhanced etching. This enhancement in etching decays exponentially with the lateral distance from the gold structure. An empirical formula for the gold-enhanced etching depth as a function of lateral distance from the edge of the gold film is extracted from the experimentally measured etch profiles. The lateral range of enhanced etching is approximately 10–20 μ m and is independent of etchant concentration. At length scales beyond a few microns, the etching enhancement is independent of the orientation with respect to the germanium crystallographic planes. The etch rate as a function of etchant concentration follows a power law with exponent smaller than 1. The observed etch rates and profiles are independent of whether the germanium substrate is n-type, p-type, or nearly intrinsic.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Genomes OnLine Database (GOLD) v.10: new features and updates

The Genomes OnLine Database (GOLD; https://gold.jgi.doe.gov/) at the Department of Energy Joint Genome Institute is a comprehensive online metadata repository designed to catalog and manage information related to (meta)genomic sequence projects. GOLD provides a centralized platform where researchers can access a wide array of metadata from its four organization levels namely Study, Organism/Biosample, Sequencing Project and Analysis Project. GOLD continues to serve as a valuable resource and has seen significant growth and expansion since its inception in 1997. With its expanded role as a collaborative platform, it not only actively imports data from other primary repositories like National Center for Biotechnology Information but also supports contributions from researchers worldwide. This collaborative approach has enriched the database with diverse datasets, creating a more integrated resource to enhance scientific insights. As genomic research becomes increasingly integral to various scientific disciplines, more researchers and institutions are turning to GOLD for their metadata needs. To meet this growing demand, GOLD has expanded by adding diverse metadata fields, intuitive features, advanced search capabilities and enhanced data visualization tools, making it easier for users to find and interpret relevant information. This manuscript provides an update and highlights the new features introduced over the last 2 years.

59 BASIC BIOLOGICAL SCIENCES↗

Extreme ultraviolet reflection efficiencies of diamond-turned aluminum, polished nickel, and evaporated gold surfaces

Measured reflection efficiencies are presented for flat samples of diamond-turned aluminum, nickel, and evaporated gold surfaces fabricated by techniques suited for EUV telescopes. The aluminum samples were 6.2-cm-diameter disks of 6061-T6, the electroless nickel samples were formed by plating beryllium disks with 7.5-microns of Kanigen. Gold samples were produced by coating the aluminum and nickel samples with 5 strips of evaporated gold. Reflection efficiencies are given for grazing angles in the 5-75 degree range. The results indicate that for wavelengths over about 100 A, the gold-coated nickel samples yield highest efficiencies. For shorter wavelengths, the nickel samples yield better efficiencies. 500 A is found to be the optimal gold thickness.

Malina, R. F.↗

The adsorption and thermal decomposition of tricresylphosphate (TCP) on iron and gold

Because tricresyl-phosphate (TCP) is a common antiwear additive in lubricants, there is great interest in its interactions with metal substrates. The TCP was allowed to adsorb on polycrystalline iron and gold at room temperature. X-ray photoelectron spectroscopy (XPS) was used to analyze the adsorbed species. The substrate was then heated in steps to 330 C, and the changes in the adsorbate were analyzed after each step. On both substrates saturation adsorption occurred at about one monolayer, but the sticking coefficient was less on gold than on iron. Comparison of the XPS spectra of TCP on each substrate with the spectrum from condensed TCP indicated nondissociative adsorption on gold, possibly by dipole-induced dipole interaction. On iron, there was apparently additional interaction between the substrate and the tolyl groups on the TCP molecule. TCP began to desorb molecularly from gold as soon as the gold was heated above room temperature. The desorption was complete by 200 C. However, when the iron substrate was heated, TCP did not desorb but decomposed between 150 and 250 C.

Wheeler, D. R.↗

Adhesion between polymers and evaporated gold and nickel films

To obtain information on the adhesion between metal films and polymeric solids, the adhesion force was measured by means of a tensile pull test. It was found that the adhesion strengths between polymeric solids and gold films evaporated on polymer substrates were (1.11 + or - 0.53) multiplied by 10(6) N/M(2) on PTFE, about 5.49 multiplied by 10(6) N/m(2) on UHMWPE, and 6.54x10(6) on 6/6 nylon. The adhesion strengths for nickel films evaporated on PTFE, UHMWPE, and 6/6 nylon were found to be a factor of 1.7 higher than those for the gold coated PTFE, UHMWPE, and 6/6 nylon. To confirm quantitatively the effect of electron irradiation on the adhesion strength between a PTFE solid and metal films, a tensile pull test was performed on the irradiated PTFE specimens, which were prepared by evaporating nickel or gold on PTFE surfaces irradiated by 2-keV electrons for various times. After irradiation, the adhesion strength increased to (4.92 + or - 0.92)x10(6) N/m(2) for nickel coated PTFE and (1.82 + or - 0.48)x10(6) N/m(2) for gold coated PTFE. The improvement in adhesion for nickel is higher than that for gold.

Yamada, Y.↗

Gold absorbing film for a composite bolometer

The principles governing the design of metal films are reviewed, with attention also given to the choice of metals. A description is then given of the characteristics of a bolometer with a gold absorbing film. It is demonstrated that gold is effective as an absorbing film for a millimeter bolometer operated at 1.5 K. At 1.5 K, gold is significantly better than bismuth since gold has a lower heat capacity for the absorbing film. At 0.3 K, gold and bismuth are both suitable. It is pointed out that at temperatures below 0.3 K, a superconducting absorbing film can have a heat capacity low enough not to dominate the heat capacity of the detector; for this reason, it may give better performance than a nonsuperconducting absorbing film.

Dragovan, M.↗

The interaction of gold with gallium arsenide

Gold and gold-based alloys, commonly used as solar-cell contact materials, are known to react readily with gallium arsenide. Experiments designed to identify the mechanisms involved in these GaAs-metal interactions have yielded several interesting results. It is shown that the reaction of GaAs with gold takes place via a dissociative diffusion process. It is shown further that the GaAs-metal reaction rate is controlled to a very great extent by the condition of the free surface of the contact metal, an interesting example of which is the previously unexplained increase in the reaction rate that has been observed for samples annealed in a vacuum environment as compared to those annealed in a gaseous ambient. A number of other hard-to-explain observations, such as the low-temperature formation of voids in the gold lattice and crystallite growth on the gold surface, are also explained by invoking this mechanism.

Weizer, Victor G.↗

Crystal growth of YBa2Cu3O(7-x) and reaction of gold crucible with Ba-Cu-rich flux

YBa2Cu3O(7-x) crystals are grown in a gold crucible by a self-flux method. The flux moves along the gold surface due to surface wetting and leaves Y123 crystals behind. The obtained crystals are clean and have a size up to two millimeters and a Tc is greater than 90 K. In an effort to recycle the used crucibles, it is found that the used gold is contaminated by copper. A CuO thin film is easily formed on the surface of the crucible that is made of the used gold. This film provides good surface wetting and a buffer layer, which reduces the reaction between gold and the Y-Ba-Cu-oxide melt.

Tao, Y. K.↗

Transmission Measurement of the Third-Order Susceptibility of Gold

Gold nanoparticle composites are known to display large optical nonlinearities. In order to assess the validity of generalized effective medium theories (EMT's) for describing the linear and nonlinear optical properties of metal nanoparticle composites, knowledge of the linear and nonlinear susceptibilities of the constituent materials is a prerequisite. In this study the inherent nonlinearity of the metal is measured directly (rather than deduced from a suitable EMT) using a very thin gold film. Specifically, we have used the z-scan technique at a wavelength near the transmission window of bulk gold to measure the third-order susceptibility of a continuous thin gold film deposited on a quartz substrate surface-modified with a self-assembled monolayer to promote adhesion and uniformity without affecting the optical properties. We compare our results with predictions which ascribe the nonlinear response to a Fermi-smearing mechanism. Further, we note that the sign of the nonlinear susceptibility is reversed from that of gold nanoparticle composites.

Smith, David D.↗

Gold Nanoparticle Labels Amplify Ellipsometric Signals

The ellipsometric method reported in the immediately preceding article was developed in conjunction with a method of using gold nanoparticles as labels on biomolecules that one seeks to detect. The purpose of the labeling is to exploit the optical properties of the gold nanoparticles in order to amplify the measurable ellipsometric effects and thereby to enable ultrasensitive detection of the labeled biomolecules without need to develop more-complex ellipsometric instrumentation. The colorimetric, polarization, light-scattering, and other optical properties of nanoparticles depend on their sizes and shapes. In the present method, these size-and-shape-dependent properties are used to magnify the polarization of scattered light and the diattenuation and retardance of signals derived from ellipsometry. The size-and-shape-dependent optical properties of the nanoparticles make it possible to interrogate the nanoparticles by use of light of various wavelengths, as appropriate, to optimally detect particles of a specific type at high sensitivity. Hence, by incorporating gold nanoparticles bound to biomolecules as primary or secondary labels, the performance of ellipsometry as a means of detecting the biomolecules can be improved. The use of gold nanoparticles as labels in ellipsometry has been found to afford sensitivity that equals or exceeds the sensitivity achieved by use of fluorescence-based methods. Potential applications for ellipsometric detection of gold nanoparticle-labeled biomolecules include monitoring molecules of interest in biological samples, in-vitro diagnostics, process monitoring, general environmental monitoring, and detection of biohazards.

Venkatasubbarao, Srivatsa↗

Dendritic gold nanoparticles and methods of synthesis

A method of producing dendritic gold nanoparticles by combining a gold precursor solution, a reducing agent, and a bifunctional peptide having an amine-rich amino acid sequence into a buffered aqueous solution in a single container, and agitating the mixture causing the formation of the dendritic gold nanoparticles having a surface with a positive charge and a second end portion of the bifunctional peptide exposed on the surface of the dendritic gold nanoparticles. The dendritic gold nanoparticles may be used to deliver therapeutic, diagnostic, and/or immunogenic amino acid sequences as portions of the bifunctional peptide.

Mao, Chuanbin↗

Source of Bright Near-Infrared Luminescence in Gold Nanoclusters

Gold nanoclusters with near-infrared (NIR) photoluminescence (PL) have great potential as sensing and imaging materials in biomedical and bioimaging applications. In this work, Au 21 (S-Adm) 15 and Au 38 S 2 (S-Adm) 20 are used to unravel the underlying mechanisms for the improved quantum yields (QY), large Stokes shifts and long PL lifetimes in gold nanoclusters. Both nanoclusters show decent PL QY. In particular, the Au 38 S 2 (S-Adm) 20 nanocluster shows a bright NIR PL at 900 nm with QY up to 15% in normal solvents (such as toluene) at ambient conditions. The relatively lower QY for Au 21 (S-Adm) 15 (4%) compared to Au 38 S 2 (S-Adm) 20 is attributed to the lowest-lying excited state being symmetry-disallowed, as evidenced by the pressure-dependent anti-spectral shift of the absorption spectra compared to PL. Yet, Au 21 (S-Adm) 15 maintains some emissive properties due to a nearby symmetry-allowed excited state. Furthermore, our results show that suppression of non-radiative decay due to the surface “lock rings” which encircle the Au kernel and the surface “lock atoms” which bridge the fundamental Au-kernel units (e.g., tetrahedra, icosahedra, etc.) is the key to obtain high QYs in gold nanoclusters. Here, the complicated excited-state processes and the small absorption coefficient of the band-edge transition lead to the large Stokes shifts and the long PL lifetimes that are widely observed in gold nanoclusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Large-Area Periodic Arrays of Atomically Flat Single-Crystal Gold Nanotriangles Formed Directly on Substrate Surfaces

The advancement of nanoenabled wafer-based devices requires the establishment of core competencies related to the deterministic positioning of nanometric building blocks over large areas. Within this realm, plasmonic single-crystal gold nanotriangles represent one of the most attractive nanoscale components but where the formation of addressable arrays at scale has heretofore proven impracticable. In this work, a benchtop process is presented for the formation of large-area periodic arrays of gold nanotriangles. The devised growth pathway sees the formation of an array of defect-laden seeds using lithographic and vapor-phase assembly processes followed by their placement in a growth solution promoting planar growth and threefold symmetric side-faceting. The nanotriangles formed in this high-yield synthesis distinguish themselves in that they are epitaxially aligned with the underlying substrate, grown to thicknesses that are not readily obtainable in colloidal syntheses, and present atomically flat pristine surfaces exhibiting gold atoms with a close-packed structure. As such, they express crisp and unambiguous plasmonic modes and form photoactive surfaces with highly tunable and readily modeled plasmon resonances. The devised methods, hence, advance the integration of single-crystal gold nanotriangles into device platforms and provide an overall fabrication strategy that is adaptable to other nanomaterials.

42 ENGINEERING↗

Site-Selective Doping and Oxidation State Control of Copper in Gold Nanorods

We report the synthesis of plasmonic gold–copper nanostructures with tunable copper spatial distribution and oxidation state. Au–Cu alloy shells were deposited in aqueous solution onto colloidal gold nanorods that functioned as seeds, and the resulting shell morphology was found to depend strongly on the nanorod aspect ratio. For relatively fat gold nanorods (16 x 31 nm), Au–Cu growth was preferentially localized near the rod midsections, forming belt-like structures, whereas for skinnier nanorods (9 x 32 nm), Au–Cu growth produced patchy surface coverage around the entire rod. The shell thickness was tuned from 1 to 4 nm; upon air exposure, thicker shells exhibited a higher Cu(I) fraction compared to the initial shell. Incorporation of the Au–Cu shell led to pronounced shifts in the plasmonic features of the gold nanorods. These tunable plasmonic Au–Cu nanorods provide a materials basis for Cu-based plasmonic materials in the context of electrochemical CO₂ reduction.

77 NANOSCIENCE AND NANOTECHNOLOGY↗