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At least 199 records · Page 11

Comparative Analysis of the Near‐ and Far‐Field Optical Response of Thin Plasmonic Nanostructures

Abstract Nanostructures made of metallic materials support collective oscillations of their conduction electrons, commonly known as surface plasmons. These modes, whose characteristics are determined by the material and morphology of the nanostructure, couple strongly to light and confine it into subwavelength volumes. Of particular interest are metallic nanostructures for which the size along one dimension approaches the nanometer or even the subnanometer scale, since such morphologies can lead to stronger light–matter interactions and higher degrees of confinement than regular three‐dimensional nanostructures. Here, the plasmonic response of metallic nanodisks of varying thicknesses and aspect ratios is investigated under far‐ and near‐field excitation conditions. It is found that, for far‐field excitation, the strength of the plasmonic response of the nanodisk increases with its thickness, as expected from the increase in the number of conduction electrons in the system. However, for near‐field excitation, the plasmonic response becomes stronger as the thickness of the nanodisk is reduced. This behavior is attributed to the higher efficiency with which a near‐field source couples to the plasmons supported by thinner nanodisks. The results of this work advance the understanding of the plasmonic response of thin metallic nanostructures, thus increasing their potential for the development of novel applications.

36 MATERIALS SCIENCE↗

Anisotropic surface potentials induced by competitive ion adsorption enable the synthesis of branched cubic Pt mesocrystals

Creation of complex nanostructured materials through oriented attachment (OA) requires the manipulation of interparticle forces, including electrostatic repulsion, which depends strongly on surface potentials and can be modified through the effect of solution environment on interfacial chemistry. Here we show that time-dependent anisotropies in surface potential driven by competitive ion adsorption can alter facet-selectivity during OA. This phenomenon enables the synthesis of branched cubic Pt mesocrystals. Initially, Pt nanoparticles attach preferentially at their {100} facets to form a well-defined cubic core. Over time, changes in ion adsorption shift the attachment preference to the {111} facets, promoting branch formation. In both stages, anisotropic surface potentials generate electrostatic torques that align the particles prior to attachment. These findings demonstrate a generalizable strategy for directing the architecture of nanomaterials through time-resolved control of interfacial chemistry during OA, offering new pathways for the design of complex mesoscale structures.

Bae, Yuna [Pacific Northwest National Laboratory (↗

Toward white light emission from plasmonic-luminescent hybrid nanostructures

We study the light emission of plasmonic-luminescent hybrid nanostructures consisting of Ag nanoparticles (NPs) embedded in europium oxide (EuO X ). The Ag NPs present a bidimensional organization in the nanostructures and they optically behave as oblate spheroids. The photoluminescence (PL) spectral response of the nanostructures evolves from a narrow red emission characteristic of Eu 3+ ions in absence of Ag NPs to a broad blue-green emission band associated with Eu 2+ ions when the layer of Ag NPs is present. This behavior is not related to a change in the Eu 2+ /Eu 3+ ratio, which is verified by compositional analysis. Instead, a detailed investigation of the PL emission of the nanostructures suggests that the coupling of the Ag NPs to the Eu 2+ ions present in the EuO X layer, which manifests itself in an efficient sensitization of these ions, enhances their broad visible emission. In particular, the longitudinal mode of the Ag NPs surface plasmon is considered to be responsible for the efficient energy transfer for the non-normal incidence excitation PL configuration used. Finally, the use of a capping amorphous Al 2 O 3 layer allows improving the robustness of hybrid nanostructures and further enhances their PL emission. These findings provide a new path to actively control the selective excitation of Eu 2+ and Eu 3+ ions via a controlled coupling with the surface plasmon resonance modes of the Ag NPs and points to these nanostructures as promising building blocks for the development of integrable white light sources.

36 MATERIALS SCIENCE↗

Formation of antireflective surfaces

Technologies are described for methods and systems effective for etching nanostructures in a substrate. The methods may comprise depositing a patterned block copolymer on the substrate. The patterned block copolymer may include first and second polymer block domains. The methods may comprise applying a precursor to the patterned block copolymer to generate an infiltrated block copolymer. The precursor may infiltrate into the first polymer block domain and generate a material in the first polymer block domain. The methods may comprise applying a removal agent to the infiltrated block copolymer to generate a patterned material. The removal agent may be effective to remove the first and second polymer block domains from the substrate. The methods may comprise etching the substrate. The patterned material on the substrate may mask the substrate to pattern the etching. The etching may be performed under conditions to produce nanostructures in the substrate.

Black, Charles T.↗

Formation of antireflective surfaces

Technologies are described for methods and systems effective for etching nanostructures in a substrate. The methods may comprise depositing a patterned block copolymer on the substrate. The patterned block copolymer may include first and second polymer block domains. The methods may comprise applying a precursor to the patterned block copolymer to generate an infiltrated block copolymer. The precursor may infiltrate into the first polymer block domain and generate a material in the first polymer block domain. The methods may comprise applying a removal agent to the infiltrated block copolymer to generate a patterned material. The removal agent may be effective to remove the first and second polymer block domains from the substrate. The methods may comprise etching the substrate. The patterned material on the substrate may mask the substrate to pattern the etching. The etching may be performed under conditions to produce nanostructures in the substrate.

Black, Charles T.↗

Accelerating Hydrogen Absorption and Desorption Rates in Palladium Nanocubes with an Ultrathin Surface Modification

Exploiting the high surface-area-to-volume ratio of nanomaterials to store energy in the form of electrochemical alloys is an exceptionally promising route for achieving high-rate energy storage and delivery. Nanoscale palladium hydride is an excellent model system for understanding how nanoscale-specific properties affect the absorption and desorption of energy carrying equivalents. Hydrogen absorption and desorption in shape-controlled Pd nanostructures does not occur uniformly across the entire nanoparticle surface. Instead, hydrogen absorption and desorption proceed selectively through high-activity sites at the corners and edges. Such a mechanism hinders the hydrogen absorption rates and greatly reduces the benefit of nanoscaling the dimensions of the palladium. To solve this, we modify the surface of palladium with an ultrathin platinum shell. This modification nearly removes the barrier for hydrogen absorption (89 kJ/mol without a Pt shell and 1.8 kJ/mol with a Pt shell) and enables diffusion through the entire Pd/Pt surface.

25 ENERGY STORAGE↗

Structural Characterization of the Platinum Nanoparticle Hydrogen-Evolving Catalyst Assembled on Photosystem I by Light-Driven Chemistry

Directed assembly of abiotic catalysts onto biological redox protein frameworks is of interest as an approach for the synthesis of biohybrid catalysts that combine features of both synthetic and biological materials. In this report, we provide a multiscale characterization of the platinum nanoparticle (NP) hydrogen-evolving catalysts that are assembled by light-driven reductive precipitation of platinum from an aqueous salt solution onto the photosystem I protein (PSI), isolated from cyanobacteria as trimeric PSI. The resulting PSI-NP assemblies were analyzed using a combination of X-ray energy-dispersive spectroscopy (XEDS), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), small-angle X-ray scattering (SAXS), and high-energy X-ray scattering with atomic pair distribution function (PDF) analyses. The results show that the PSI-supported NPs are approximately 1.8 nm diameter disk-shaped particles that assemble at discrete sites with 145 Å separation. This separation is too large to be consistent with NP nucleation and growth at a site adjacent to the F B cofactor site. Instead, we suggest a mechanism for NP growth at hydrophobic sites on the PSI stromal surface. The NPs photoreductively assembled on the PSI stromal surface are found to be analogous to the nanostructures produced by successive cycles of atomic layer deposition (ALD) of platinum onto 40 nm porous anodic alumina oxide supports, although the mechanisms for nucleation appear to differ. In conclusion, this work establishes a foundation for the investigation of the reductive assembly of abiotic metal catalysts at sites connected to photochemically reducing equivalent production in PSI.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of the interfacial bonding strength between hafnia and silica layers deposited by electron-beam evaporation

Factors contributing to the mechanical strength of multilayer optical coatings involving alternating layers of electron-beam evaporated hafnia and silica is investigated. It is observed that upon rupture resulting from nanosecond laser damage, fragments consisting of layer pairs are produced. These pairs are formed as a result of a strong asymmetry in adhesion strength between interfaces, leading to preferential delamination at interfaces where silica is deposited on hafnia, and not the reverse, despite the fact that both interface types consist of the same pair of materials. The observed disparity in adhesion strength was further studied using nanomechanical scratch tests, revealing loads at which fracture occurs, and fracture morphology, both of which are highly dependent on deposition order. Based on these measurements, along with the morphological analysis of the nanostructure of the coatings, we conclude that the surface microstructure in each coating layer affects its adhesion strength with the succeeding layer. The findings outlined here are particularly relevant to the production of large aperture, high-performance optics designed for use in next-generation lasers.

adhesion strength↗

Morphological Modulation of TiO 2 Nanotube via Optimal Anodization Condition for Solar Water Oxidation

With the depletion of fossil fuels and the rising global demand for energy, photoelectrochemical (PEC) water splitting presents a promising solution to avert an energy crisis. Titanium dioxide (TiO 2 ), an n -type semiconductor, has gained popularity as a photoanode due to its remarkable PEC properties. Nevertheless, inherent challenges such as a wide band gap (~3.2 eV), charge recombination, and slow oxygen evolution reaction (OER) rates at the surface limit its practical application by constraining light absorption. To overcome these limitations, we have developed TiO 2 nanotubes (NTs) using a facile anodization method. This study examines the impact of anodization growth parameters on solar water oxidation performance. Specifically, TiO 2 NTs with modified anodization time (referred to as TiO 2 -6) showed a 3.5-fold increase in photocurrent density compared to the as-grown TiO 2 NTs. Furthermore, electrochemical analyses, such as electrochemical impedance spectroscopy (EIS), indicated a significant decrease in charge transfer resistance following the adjustment of on-off anodization time. Additionally, the TiO 2 -6 photoanode demonstrated a higher electrochemically active surface area (ECSA) than other samples. Therefore, optimal nanostructuring parameters are crucial for enhancing the PEC properties of TiO 2 NTs. Overall, our findings offer valuable insights for fabricating high-quality TiO 2 NTs photoanodes, contributing to developing efficient PEC systems for sustainable energy production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optimizing the Fabrication of Electrospun Nanofibrous Membrane Using Fractional Factorial Design

Electrospinning, a simple and easily tunable technique that utilizes the force balance between the electrostatic force and the solution surface tension to fabricate membranes out of 1D nanostructured fibers, has garnered much interest especially from the nanotechnology community. Depending on the morphology of the fibers, electrospun membrane has found its way in a wide range of applications, such as oil-water separation, desalination, tissue engineering, and batteries. During an electrospinning process, many factors can affect the morphology of the products, such as viscosity of the solution, voltage supply, discharge distance, feed rate of the solution, and electrospinning time. In this work, we investigated the impacts of the most important parameters on the morphology of electrospun fibrous membrane based on the fractional factorial design. We evaluated the electrospun fibrous membrane morphology using scanning electron microscopy (SEM) and capillary flow porometry. Poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) was chosen for the current study due to its interesting and versatile functionalities including superior hydrophobicity, high free volume, and piezoelectricity. This work provides valuable insight for the fabrication of electrospun membranes, especially for tailoring membrane properties in accordance with any targeted applications.

Zhao, Yajing↗

Catalyst comprising Pt, Ni, and Cr

Catalysts comprising nanostructured elements comprising microstructured whiskers having an outer surface at least partially covered by a catalyst material comprising at least 90 atomic percent collectively Pt, Ni, and Cr, wherein the Pt is present in a range from 32.4 to 35.8 atomic percent, the Ni is present in a range from 57.7 to 63.7 atomic percent, and the Cr is present in a range from 0.5 to 10.0 atomic percent, and wherein the total atomic percent of Pt, Ni, and Cr equals 100. Catalyst described herein are useful, for example, in fuel cell membrane electrode assemblies.

Steinbach, Andrew J. L.↗

Triboelectric nanogenerator for harvesting energy from water

An apparatus including a first member including a first electrode, a second member coupled to the first member about an axis, including a second electrode, and a surface layer between the first electrode and the second electrode, the second member is rotatable with respect to the axis by an energy flow to change triboelectric charges on the electrodes, and to affect a flow of electrons between the electrodes. A self-powered sensor for detecting a chemical including a generator having an electrode, and a superhydrophobic surface layer for receiving an energy flow carrying triboelectric charges, the surface layer includes a TiO 2 layer with nanostructures, and a power indicator indicative of whether the chemical is present based on power output of the triboelectric generator, the energy flow is a solution flow, the solution comprising the chemical and water, and the chemical removes at least one triboelectric charge from the water.

Wang, Zhong Lin↗

Morphology and chemical behavior of model CsO x /Cu 2 O/Cu(111) nanocatalysts for methanol synthesis: Reaction with CO 2 and H 2

Cs is a promoter of Cu-based catalysts for the synthesis of alcohols from CO 2 hydrogenation. Scanning tunneling microscopy and ambient-pressure x-ray photoelectron spectroscopy were used to study the morphology and chemical properties of surfaces generated by the deposition of cesium on Cu 2 O/Cu(111) and Cu(111) substrates. CsO x nanostructures were formed after Cs metal was deposited on Cu 2 O/Cu(111) at 300 K. The formed CsO x protrude over the surface of copper oxide by 2–4 Å, with the dimension at the base of the nanostructures being in the range of 1–3 nm. Heating to elevated temperature induced significant changes in the size and dispersion of the CsO x nanostructures, and there was a clear reconstruction of the copper oxide substrate, which then exhibited long range order with a hexagonally packed structure. The as-deposited and annealed surfaces of CsO x /Cu 2 O/Cu(111) were more reactive toward CO 2 than plain Cu 2 O/Cu(111) or clean Cu(111). Yet, none of them were stable in the presence of H 2 , which fully reduced the copper oxide at 400–450 K. In CsO x /Cu(111), the CsO x nanoclusters were dispersed all over the metallic copper in no particular order. The CsO x species had an average width of 2 nm and ~1 Å height. The CsO x /Cu(111) systems exhibited the highest activity for the binding and dissociation of CO 2 , indicating that the CsO x -copper interface plays a key role in alcohol synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quasi-Two-Dimensional Earth-Abundant Bimetallic Electrocatalysts for Oxygen Evolution Reactions

The extremely large surface area offered by quasi-two-dimensional (2D) nanostructures is a great advantage for catalytic applications. While bimetallic materials have been discovered as a group of promising catalysts for electrochemical water splitting, a facile and reliable synthesis approach toward 2D morphology to fully release its electrochemical catalytic potential is still lacking. In this work, bimetallic Co–Mo–O ultrathin nanosheets were synthesized by ionic layer epitaxy with controlled composition ratio. The Co–Mo–O nanosheets exhibited a quadrangle shape with a uniform thickness of ~2.5 nm. This 2D morphology largely enriched the surface catalytic active site ratio. Particularly, nanosheets with 2:1 Co-to-Mo ratio showed a substantially enhanced OER catalytic activity with a 3 orders of magnitude higher mass activity compared to benchmark IrO 2 and RuO 2 in an alkaline environment. Furthermore, this study introduces a promising possibility for creating high-performance electrocatalysts from 2D bimetallic materials with a high efficiency for material utilization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Construction of Lattice Strain in Bimetallic Nanostructures and Its Effectiveness in Electrochemical Applications

Bimetallic nanocrystals (NCs), associated with various surface functions such as ligand effect, ensemble effect, and strain effect, exhibit superior electrocatalytic properties. The stress-induced surface strain effect can alter binding strength between the surface active sites and reactants as well as their intermediates, and the electrochemical performance of bimetallic NCs can be significantly facilitated by the lattice-strain modification via their morphologies, sizes, shell-thickness, surface defectiveness as well as compositions. Here in this review, an overview of fundamental principles, characterization techniques, and quantitative determination of the surface lattice strain is provided. Various strategies and synthesis efforts on creating lattice-strain-engineered bimetallic NCs, including the de-alloying process, atomic layer-by-layer deposition, thermal treatment evolution, one-pot synthesis, and other efforts are also discussed. It is further outlined how the lattice strain effect promotes electrochemical catalysis through the selected case studies. The reactions on oxygen reduction reaction, small molecular oxidation, water splitting reaction, and electrochemical carbon dioxide reduction reactions are focused. In particular, studies of lattice strain arisen from core–shell nanostructure and defectiveness are highlighted. Lastly, the potential challenges are summarized and the prospects of lattice-strain-based engineering on bimetallic nanocatalysts with suggestion and guidance of the future electrocatalyst design are envisioned.

36 MATERIALS SCIENCE↗

Battery anode design: From 1D nanostructure to 3D nanoarchitecture – Enabling next-generation energy storage technology

Recently, many studies have reported the efficacy of 1D silicon nanostructures as anode materials (mostly nanowires) due to their large surface to volume ratio which could be an advantage in terms of charging kinetics. Anode design is a crucial factor for the further development of lithium-ion battery (LIB) technology, especially in terms of achieving the high charging rate performance, as typically needed in electric vehicles (EV). 3D nanostructures have been identified as the key to dramatically enhanced charging rate of LIB, in addition to the change of materials (from carbon-based anode to silicon-based). However, existing fabrication methodologies for 3D nanostructures are inherently expensive – using advanced lithography techniques or other nanopatterning methodologies, as well as using additive manufacturing approaches. Electrospinning (as an integrated additive manufacturing methodology) may be used to produce low-cost 3D-printed fiber structures. Here, in the present study, we demonstrate the groundwork in this field of research in the past 3–4 years, which would allow the extension of this special additive manufacturing approach to reach nanoscale 3D-printed fiber structures more economically and with scalability for manufacturing. This would pave the way to achieve the order of magnitude increase in battery charging rate as needed to realize the vision of the electrification of mobility/transportation.

25 ENERGY STORAGE↗

Inversion of coherent surface scattering images via deep learning network

Coherent surface scattering imaging is a powerful tool for imaging a surface/interface of a thin nanostructure deposited on an opaque substrate. A mathematical conversion of an object image from a scattering pattern is essential for coherent surface scattering imaging to visualize structures of specimens. It has been achieved by using phase retrieval algorithms requiring oversampling in scattering patterns and employing alternating projection approaches. It is a computationally challenging and time-consuming process. In this paper, we demonstrate CSSI-NN, which is a deep learning neural network model to predict images of objects from scattering intensities in coherent surface scattering imaging. This model allowing for the instant outcome from scattering patterns would be tremendously beneficial not only for effective experiments but also for data analysis of phase retrieval.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Atomic‐Scale Surface Imaging of Bulk Epitaxial CsPbBr 3 Perovskite Single Crystals on Mica Using Light Assisted Scanning Tunneling Microscopy at Low‐Temperature (80 K)

Epitaxial single-crystalline CsPbBr 3 perovskite films on mica, prepared ex situ, are explored using a low-temperature scanning tunneling microscope (STM) by probing the unoccupied electronic states of their surface in ultra-high vacuum (UHV) at 80 K. Light-assisted STM measurements under a broadband illumination with visible light were employed to enhance and stabilize surface conductivity. STM imaging across the surface of macroscopic bulk CsPbBr 3 films reveals large flat terraces characterized by a specific type of surface reconstruction, consisting of parallel rows of U-shaped atomic nanostructures. These structures are spaced by 12 Å and exhibit an internal feature size of 5.1 Å. Density functional theory (DFT) calculations reproduce the experimental observations and reveal a competition between different orthorhombic CsPbBr 3 (110) surface reconstructions: a Cs-rich structure, identified as the most energetically stable, and three alternative Pb–Br-rich reconstructions, which are slightly higher in energy yet remain consistent with the STM data. Additional analyses that explicitly account for the mica substrate exclude the cubic CsPbBr 3 phase and other orthorhombic surface orientations, while showing that variations in the mica surface termination do not alter the preferred CsPbBr 3 (110) reconstruction. In conclusion, this combined approach thereby confirms our assignment and resolves previous STM interpretations of CsPbBr 3 .

36 MATERIALS SCIENCE↗