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At least 19 records

Evoking ordered vacancies in metallic nanostructures toward a vacated Barlow packing for high-performance hydrogen evolution

Metallic nanostructures are commonly densely packed into a few packing variants with slightly different atomic packing factors. The structural aspects and physicochemical properties related with the vacancies in such nanostructures are rarely explored because of lack of an effective way to control the introduction of vacancy sites. Highly voided metallic nanostructures with ordered vacancies are however energetically high lying and very difficult to synthesize. Here, we report a chemical method for synthesis of hierarchical Rh nanostructures (Rh NSs) composed of ultrathin nanosheets, composed of hexagonal close-packed structure embedded with nanodomains that adopt a vacated Barlow packing with ordered vacancies. The obtained Rh NSs exhibit remarkably enhanced electrocatalytic activity and stability toward the hydrogen evolution reaction (HER) in alkaline media. Theoretical calculations reveal that the exceptional electrocatalytic performance of Rh NSs originates from their unique vacancy structures, which facilitate the adsorption and dissociation of H 2 O in the HER.

36 MATERIALS SCIENCE↗

Method for making metal-nanostructured carbon composites

A method for making covetic metal-nanostructured carbon composites or compositions is described herein. This method is advantageous, in that it provides substantially oxygen-free covetic materials and allows precise control of the composition of the covetic material to be produced. The method comprises introducing carbon into a molten metal in a heated reactor under low oxygen partial pressure, while passing an electric current through the molten metal. The reactor is heated at a temperature sufficient to form a network of nanostructured carbon within a matrix of the metal. After heating the covetic material is recovered from the reactor.

Balachandran, Uthamalingam↗

Versatile stochastic model for predictive KMC simulation of fcc metal nanostructure evolution with realistic kinetics

Stochastic lattice-gas models provide the natural framework for analysis of the surface diffusion-mediated evolution of crystalline metal nanostructures on the appropriate time scale (often 10 1 –10 4 s) and length scale. Model behavior can be precisely assessed by kinetic Monte Carlo simulation, typically incorporating a rejection-free algorithm to efficiently handle the broad range of Arrhenius rates for hopping of surface atoms. The model should realistically prescribe these rates, or the associated barriers, for a diversity of local surface environments. However, commonly used generic choices for barriers fail, even qualitatively, to simultaneously describe diffusion for different low-index facets, for terrace vs step edge diffusion, etc. We introduce an alternative Unconventional Interaction–Conventional Interaction formalism to prescribe these barriers, which, even with few parameters, can realistically capture most aspects of behavior. Here, the model is illustrated for single-component fcc metal systems, mainly for the case of Ag. It is quite versatile and can be applied to describe both the post-deposition evolution of 2D nanostructures in homoepitaxial thin films (e.g., reshaping and coalescence of 2D islands) and the post-synthesis evolution of 3D nanocrystals (e.g., reshaping of nanocrystals synthesized with various faceted non-equilibrium shapes back to 3D equilibrium Wulff shapes).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Competing Classical and Quantum Effects in Shape Relaxation of a Metallic Nanostructure

We demonstrate for the first time that the quantum size effect (QSE) plays a competing role along side the classical thermodynamic effect in the shape relaxation of a small metallic island. Together, these effects transforms a lead(Pb) island grown on Si(111) substrate from its initially flattop faceted morphology to a peculiar ring-shape island, a process catalysed by the tip electric field of a scanning tunnelling microscope (STM). We shall show for the first time how QSE affects the relaxation process dynamically. In particular, it leads to a novel strip-flow growth and double-step growth on selective strips of a plateau inside the ring, defined by the substrate steps more than 60?0?3 below. It appears that atoms diffusing on the plateau can clearly (sub i)(deg)sense(sub i)+/- the quantized energy states inside the island and have preferentially attached to regions that further reduces the surface energy as a result of the QSE, limiting its own growth and stabilizing the ring shape. The mechanism proposed here offers a sound explanation for ring shape metal and semiconductor islands observed in other systems as well.

Chen, Dongmin↗

Micro- and Nanostructured Metal Oxide Chemical Sensors for Volatile Organic Compounds

Aeronautic and space applications warrant the development of chemical sensors which operate in a variety of environments. This technical memorandum incorporates various kinds of chemical sensors and ways to improve their performance. The results of exploratory investigation of the binary composite polycrystalline thick-films such as SnO2-WO3, SnO2-In2O3, SnO2-ZnO for the detection of volatile organic compound (isopropanol) are reported. A short review of the present status of the new types of nanostructured sensors such as nanobelts, nanorods, nanotube, etc. based on metal oxides is presented.

Alim, M. A.↗

Effect of Random Nanostructured Metallic Environments on Spontaneous Emission of HITC Dye

We have studied emission kinetics of HITC laser dye on top of glass, smooth Au films, and randomly structured porous Au nanofoams. The observed concentration quenching of luminescence of highly concentrated dye on top of glass (energy transfer to acceptors) and the inhibition of the concentration quenching in vicinity of smooth Au films were in accord with our recent findings. Intriguingly, the emission kinetics recorded in different local spots of the Au nanofoam samples had a spread of the decay rates, which was large at low dye concentrations and became narrower with increase of the dye concentration. We infer that in different subvolumes of Au nanofoams, HITC molecules are coupled to the nanofoams weaker or stronger. The inhibition of the concentration quenching in Au nanofoams was stronger than on top of smooth Au films. This was true for all weakly and strongly coupled subvolumes contributing to the spread of the emission kinetics. The experimental observations were explained using theoretical model accounting for change in the Förster radius caused by the strong energy transfer to metal.

36 MATERIALS SCIENCE↗

Dominant Energy Carrier Transitions and Thermal Anisotropy in Epitaxial Iridium Thin Films

High aspect ratio metal nanostructures are commonly found in a broad range of applications such as electronic compute structures and sensing. The self-heating and elevated temperatures in these structures, however, pose a significant bottleneck to both the reliability and clock frequencies of modern electronic devices. Any notable progress in energy efficiency and speed requires fundamental and tunable thermal transport mechanisms in nanostructured metals. Here, in this work, time-domain thermoreflectance is used to expose cross-plane quasi-ballistic transport in epitaxially grown metallic Ir(001) interposed between Al and MgO(001). Thermal conductivities ranges from roughly 65 (96 in-plane) to 119 (122 in-plane) W m -1 K -1 for 25.5–133.0 nm films, respectively. Further, low defects afforded by epitaxial growth are suspected to allow the observation of electron–phonon coupling effects in sub-20 nm metals with traditionally electron-mediated thermal transport. Via combined electro-thermal measurements and phenomenological modeling, the transition is revealed between three modes of cross-plane heat conduction across different thicknesses and an interplay among them: electron dominant, phonon dominant, and electron–phonon energy conversion dominant. The results substantiate unexplored modes of heat transport in nanostructured metals, the insights of which can be used to develop electro-thermal solutions for a host of modern microelectronic devices and sensing structures.

36 MATERIALS SCIENCE↗

Process for the preparation of metal-containing nanostructured films

Metal-containing nanostructured films are prepared by electrodepositing a metal-containing composition within the pores of a mesoporous silica template to form a metal-containing silica nanocomposite. The nanocomposite is annealed to strengthen the deposited metal-containing composition. The silica is then removed from the nanocomposite, e.g., by dissolving the silica in an etching solution to provide a self-supporting metal-containing nanostructured film. The nanostructured films have a nanowire or nanomesh architecture depending on the pore structure of the mesoporous silica template used to prepare the films.

Lu, Yunfeng↗

Chemical Sensors Based on Metal Oxide Nanostructures

This paper is an overview of sensor development based on metal oxide nanostructures. While nanostructures such as nanorods show significan t potential as enabling materials for chemical sensors, a number of s ignificant technical challenges remain. The major issues addressed in this work revolve around the ability to make workable sensors. This paper discusses efforts to address three technical barriers related t o the application of nanostructures into sensor systems: 1) Improving contact of the nanostructured materials with electrodes in a microse nsor structure; 2) Controling nanostructure crystallinity to allow co ntrol of the detection mechanism; and 3) Widening the range of gases that can be detected by using different nanostructured materials. It is concluded that while this work demonstrates useful tools for furt her development, these are just the beginning steps towards realizati on of repeatable, controlled sensor systems using oxide based nanostr uctures.

Hunter, Gary W.↗

Exploring the Structural Origins of Optically Efficient One-Dimensional Lead Halide Perovskite Nanostructures

Metal halide perovskites have excellent optoelectronic properties. This study aims to determine how the optoelectronic properties of a model perovskite, cesium lead bromide (CsPbBr3), change with length and thickness in one dimension (1D). By examining the photophysics of CsPbBr3 quantum dots (QDs), nanowires (NWs), and nanorods (NRs), we observe the influence of confinement, exciton diffusion, and trapping on their optical properties. Our findings reveal that exciton diffusion to trap states limits the photoluminescence quantum yield (PLQY) of 1D CsPbBr3 in the weakly confined regime (8-14 nm) and explains their long-lived exciton dynamics, while enhanced radiative rates contribute to achieving near-unity PLQY in the strongly confined regime (<7 nm). Consequently, blue-emitting, 2.4 nm-thick CsPbBr3 NRs were 3.6X more emissive than the conventional CsPbBr3 QDs. This study underscores how structural optimization can improve the optoelectronic performance of CsPbBr3 and provides insight into the complex interplay of radiative and nonradiative processes in 1D ionic semiconductors.

Oddo, Alexander M↗

Nanostructured mixed metal oxides as catalysts and method of making thereof

A method of forming a metal oxide material having a rod shape or polyhedral nanostructure includes preparing a first reverse micro-emulsion system comprising an aqueous precipitating agent dispersion and a second reverse micro-emulsion system containing an aqueous metal salt dispersion; combining the micro-emulsions together to initiate a reaction; allowing the reaction to continue to form a product mixture comprising a metal oxide gel and aqueous media; separating the metal oxide gel from the aqueous media; collecting the metal oxide gel; and calcining the metal oxide gel to form the metal oxide material. The metal oxide material corresponds to the chemical formula of La2MxNi1-xO4, Pr2-yAyNiO4, or La2-zDzNiO4, wherein M is copper, cobalt, iron, manganese, chromium, aluminum, or platinum; A is lanthanum or neodymium; D is calcium, barium or strontium; x ranges from 0 to 1; y ranges from 0 to 2; and z ranges from 0 to 0.25.

Nikolla, Eranda↗

Metallo-graphene nanocomposites and methods for using metallo-graphene nanocomposites for electromagnetic energy conversion

Nanocomposites in accordance with many embodiments of the invention can be capable of converting electromagnetic radiation to an electric signal, such as signals in the form of current or voltage. In some embodiments, metallic nanostructures are integrated with graphene material to form a metallo-graphene nanocomposite. Graphene is a material that has been explored for broadband and ultrafast photodetection applications because of its distinct optical and electronic characteristics. However, the low optical absorption and the short carrier lifetime of graphene can limit its use in many applications. Nanocomposites in accordance with various embodiments of the invention integrates metallic nanostructures, such as (but not limited to) plasmonic nanoantennas and metallic nanoparticles, with a graphene-based material to form metallo-graphene nanostructures that can offer high responsivity, ultrafast temporal responses, and broadband operation in a variety of optoelectronic applications.

Jarrahi, Mona↗

In Situ TEM Study of Radiation Resistance of Metallic Glass–Metal Core–Shell Nanocubes

Radiation damage can cause significantly more surface damage in metallic nanostructures than bulk materials. Structural changes from displacement damage compromise the performance of nanostructures in radiation environments such as nuclear reactors and outer space, or used in radiation therapy for biomedical treatments. As such, it is important to develop strategies to prevent this from occurring if nanostructures are to be incorporated into these applications. In this work, in situ transmission electron microscope ion irradiation was used to investigate whether a metallic glass (MG) coating mitigates sputtering and morphological changes in metallic nanostructures. Dislocation-free Au nanocubes and Au nanocubes coated with a Ni–B MG were bombarded with 2.8 MeV Au 4+ ions. The formation of internal defects in bare Au nanocubes was observed at a fluence of 7.5 × 10 11 ions/cm 2 (0.008 dpa), and morphological changes such as surface roughening, rounding of corners, and formation of nanofilaments began at 4 × 10 12 ions/cm 2 (0.04 dpa). In contrast, the Ni–B MG-coated Au nanocubes (Au@NiB) showed minimal morphological changes at a fluence of 1.9 × 10 13 ions/cm 2 (0.2 dpa). Finally, the MG coating maintains its amorphous nature under all irradiation conditions investigated.

36 MATERIALS SCIENCE↗