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At least 937 records · Page 52

Resonance modes, cavity field enhancements, and long-range collective photonic effects in periodic bowtie nanostructures

The discovery of single-molecule sensitivity via surfaceenhanced Raman scattering on resonantly excited noble metal nanoparticles has brought an increasing interest in its applications to the molecule detection and identification. Periodic gold bowtie nanostructures have recently been shown to give a large enhancement factor sufficient for single molecule detection. In this work, we simulate the plasmon resonance for periodic gold bowtie nanostructures. The difference between the dipole and the quadrupole resonances is described by examining the magnitude and phase of electric field, the bound surface charge, and the polarization. The gap size dependence of the field enhancement can be interpreted by considering cavity field enhancement. Also, additional enhancement is obtained through the long-range collective photonic effect when the bowtie array periodicity matches the resonance wavelength.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Confined cooperative self-assembly and synthesis of optically and electrically active nanostructures : final LDRD report

In this project, we developed a confined cooperative self-assembly process to synthesize one-dimensional (1D) j-aggregates including nanowires and nanorods with controlled diameters and aspect ratios. The facile and versatile aqueous solution process assimilates photo-active macrocyclic building blocks inside surfactant micelles, forming stable single-crystalline high surface area nanoporous frameworks with well-defined external morphology defined by the building block packing. Characterizations using TEM, SEM, XRD, N{sub 2} and NO sorption isotherms, TGA, UV-vis spectroscopy, and fluorescence imaging and spectroscopy indicate that the j-aggregate nanostructures are monodisperse and may further assemble into hierarchical arrays with multi-modal functional pores. The nanostructures exhibit enhanced and collective optical properties over the individual chromophores. This project was a small footprint research effort which, nonetheless, produced significant progress towards both the stated goal as well as unanticipated research directions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Nanostructured Activated Carbon for Hydrogen Storage Project Final Technical Report (May 2, 2005-Dec. 31, 2012)

Development of a nanostructured synthetic carbons materials that have been synthesized by thermal-decomposition of aromatic rich polyether such as poly(ether ether ketone) (PEEK) is reported. These polymers based nanostructured carbons efficacious for gas adsorption and storage and have Brunauer-Emmett-Teller (BET) surface area of more than 3000 m 2 /g, and with average pore diameter of < 2nm. Surface-area, pore characteristics, and other critical variables for selecting porous materials of high gas adsorption capacities are presented. Analysis of the fragments evolved under various carbonization temperatures, and the correlation between the activation and carbonization temperatures provides a mechanistic perspective of the pore evolution during activation. Correlations between gas (N 2 and H 2 ) adsorption capacity and porous texture of the materials have been established. The materials possess excellent hydrogen storage properties, with hydrogen storage capacity up to 7.4 wt% (gravimetric) and ~ 45 g H 2 L-1 (volumetric) at -196oC and 6.0 MPa.

08 HYDROGEN↗

Precursor Derived Nanostructured Si-C-X Materials for Nuclear Applications. Final Report, October 2010 - September 2014

Polymer derived ceramic route is an attractive approach to make structural materials with unique nanostructures that have very desirable high temperature properties. Processing techniques to make a variety of needed shapes and forms (e.g. coatings, matrices for fiber reinforced composites, porous ceramics) have been developed. With appropriate high temperature processing, the precursors can be converted to nano-crystalline materials. In this collaborative project, we investigated the processing, stability and properties of nanostructured Si-C materials, derived from polymeric precursors, and their performance under conditions appropriate for nuclear energy applications. All the milestones of the project were accomplished. Some of the results are being currently analyzed and additional papers being prepared in which support from NEUP will be acknowledged. So far, eight peer-reviewed papers have been published and one invention disclosure made. In this report, we summarize the major findings of this project.

36 MATERIALS SCIENCE↗

DOE-EFRC Center on Nanostructuring for Efficient Energy Conversion (CNEEC)

CNEEC’s mission has been to understand how nanostructuring of materials can enhance efficiency for solar energy conversion to produce hydrogen fuel and to solve fundamental cross-cutting problems. The overarching hypothesis underlying CNEEC research was that controlling, synthesizing and modifying materials at the nanometer scale increases the efficiency of energy conversion and storage devices and systems. In this pursuit, we emphasized the development of functional nanostructures that are based primarily on earth abundant and inexpensive materials.

08 HYDROGEN↗

Nanostructured Materials for High Efficiency Low Cost Solution-Processed Photovoltaics

The goal of the project was to develop a suite of materials coupled with processing technologies aimed at the fabrication of entirely solution-processed photovoltaic devices. Most of the emphasis in terms of innovation was placed on the transparent electrodes, widely considered a critical component of the solar cell in terms of cost and performance. The active layer technologies proposed hinged on the fabrication and deposition of semiconducting nanoparticles. The electrode development hit all the milestones proposed: by the end of the grant we were able to fabricate transparent and flexible electrodes with transmission over the solar spectrum higher than 85% and sheet resistance lower than 10 Ω/square. To the best of our knowledge, this is the highest-performance transparent electrode reported. Furthermore these electrodes were deposited by spray-coating, a large-area, low-cost deposition techniques. Hence the first main goal of the proposal, which was to find an alternative to ITO was successfully achieved. Organic photovoltaic devices were made with these electrodes having a performance indistinguishable from that of devices made on ITO (the industry standard), e.g. ~5% for P3HT:PCBM cells. We also innovated in the active-area part of the device where semiconducting inks were designed rather than nanoparticle suspensions. The process we selected, called air-stable ink rolling (AIR) allowed to deposit well-controlled films of ternary and quaternary II-VI semiconductors. Developing a new technology from scratch proved to be more challenging than anticipated and therefore we were not able to demonstrate a fully integrated device using our nanostructured high-performance transparent electrodes as well as AIR active layers. As a result, we did not achieve the second main goal of the proposal, which was to fabricate an entire cell using nanostructured materials. We were able to develop the components separately but did not integrate them in a device.

14 SOLAR ENERGY↗

Quantitative Characterization of Nanostructured Materials

The two-and-a-half day symposium on the "Quantitative Characterization of Nanostructured Materials" will be the first comprehensive meeting on this topic held under the auspices of a major U.S. professional society. Spring MRS Meetings provide a natural venue for this symposium as they attract a broad audience of researchers that represents a cross-section of the state-of-the-art regarding synthesis, structure-property relations, and applications of nanostructured materials. Close interactions among the experts in local structure measurements and materials researchers will help both to identify measurement needs pertinent to real-world materials problems and to familiarize the materials research community with the state-of-the-art local structure measurement techniques. We have chosen invited speakers that reflect the multidisciplinary and international nature of this topic and the need to continually nurture productive interfaces among university, government and industrial laboratories. The intent of the symposium is to provide an interdisciplinary forum for discussion and exchange of ideas on the recent progress in quantitative characterization of structural order in nanomaterials using different experimental techniques and theory. The symposium is expected to facilitate discussions on optimal approaches for determining atomic structure at the nanoscale using combined inputs from multiple measurement techniques.

36 MATERIALS SCIENCE↗

Obstacles to applications of nanostructured thermoelectric alloys

A major theme in thermoelectric research is based on controlling the formation of nanostructures that occur naturally in bulk intermetallic alloys through various types of thermodynamic phase transformation processes (He et al., 2013). The question of how such nanostructures form and why they lead to a high thermoelectric figure of merit (zT) are scientifically interesting and worthy of attention. However, as we discuss in this opinion, any processing route based on thermodynamic phase transformations alone will be difficult to implement in thermoelectric applications where thermal stability and reliability are important. Attention should also be focused on overcoming these limitations through advanced post-processing techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sustainable and Green Production of Nanostructured Cellulose by a 2-Step Mechano-Enzymatic Process

Nanostructured cellulose (NC) represents an emerging sustainable biomaterial for diverse biotechnological applications; however, its production requires hazardous chemicals that render the process ecologically unfriendly. Using commercial plant-derived cellulose, an innovative strategy for NC production based on the combination of mechanical and enzymatic approaches was proposed as a sustainable alternative to conventional chemical procedures. After ball milling, the average length of the fibers was reduced by one order of magnitude (down to 10–20 μm) and the crystallinity index decreased from 0.54 to 0.07–0.18. Moreover, a 60 min ball milling pre-treatment followed by 3 h Cellic Ctec2 enzymatic hydrolysis led to NC production (15% yield). Analysis of the structural features of NC obtained by the mechano-enzymatic process revealed that the diameters of the obtained cellulose fibrils and particles were in the range of 200–500 nm and approximately 50 nm, respectively. Interestingly, the film-forming property on polyethylene (coating ≅ 2 μm thickness) was successfully demonstrated and a significant reduction (18%) of the oxygen transmission rate was obtained. Altogether, these findings demonstrated that nanostructured cellulose could be successfully produced using a novel, cheap, and rapid 2-step physico-enzymatic process that provides a potential green and sustainable route that could be exploitable in future biorefineries.

59 BASIC BIOLOGICAL SCIENCES↗

Effect of anharmonicity of interatomic potential on strain distribution in semiconductor nanostructures

Experiments and theory have shown that the energy spectrum of nanostructures is extremely sensitive to the built-in strain. Knowledge of the strain distribution is therefore Experiments and theory have shown that the energy spectrum of nanostructures is extremely sensitive to the built-in strain. Knowledge of the strain distribution is therefore of utmost importance for the design of optical devices with prescribed light emission spectrum.

nanostructures↗

Antiferromagnetic domain reconfiguration in embedded LaFeO3 thin film nanostructures

Using photoemission electron microscopy in combination with X-ray magnetic linear dichroism, we report reconfiguration upon nanostructuring of the antiferromagnetic domain structure in epitaxial LaFeO3 thin films. Antiferromagnetic (AFM) nanoislands were synthesized using a dedicated process, devised to define nanostructures with magnetic order embedded in a paramagnetic matrix. Significant impact on the AFM domain configuration was observed. Extended domains were found to form along edges parallel to the in-plane 100 crystalline axes of the cubic substrate, with their AFM spin axis parallel to the edge. No such edge-imposed domain configuration was found for nanoislands defined with the edges at 45 with the in-plane crystalline axes. Epitaxial constraints on the film crystalline structure appear to play an important role in the formation of the edge-bound extended AFM domains. The data indicate a magnetostatic origin of this domain reconfiguration.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

High resolution electron microscopy of GaAs capped GaSb nanostructures

We show in this work that GaAs capping of 2 ML of GaSb grown by molecular beam epitaxy results in the formation of very small (with heights of about 1 nm) GaAsxSb1 x nanostructures surrounded by a GaAs rich layer. This conclusion is obtained by analyzing the morphology of the GaAsxSb1 x nanostructures by high resolution scanning transmission electron microscopy in Z-contrast mode. This result shows that a significant fraction of the Sb atoms must segregate along the growth direction during the GaAs capping process.

36 MATERIALS SCIENCE↗

High-Speed Direct Laser Writing of Silver Nanostructures via Two-Photon Reduction

Despite the widespread use of metallic nanostructures in several emerging applications, high-throughput template-free fabrication techniques that are capable of patterning arbitrarily complex nanostructures are lacking. Two-photon reduction-based direct laser writing is a promising technique due to its ability to fabricate geometrically intricate metallic structures with sub-diffraction nanoscale features. Unfortunately, the extremely low writing speed of ≈10 μm s -1 makes this process impractical for large-scale manufacturing. The operating speed is currently limited by a lack of photoresist materials that can operate under high-speed writing conditions. Herein, a silver-containing aqueous photoresist recipe is presented that increases the writing speed to 1 cm s -1 while maintaining the ability to fabricate sub-diffraction silver nanowires as thin as 500 nm. In addition, the electrical conductivity of the printed silver is within one-fifth that of bulk silver. Strikingly, it is demonstrated here that the conventional design rule of using surfactants to promote high-quality printing is faulty under high-speed conditions. Instead, surfactants limit the throughput and are eliminated to enable high-speed writing. The 1000× throughput scale-up presented here significantly improves our ability to transition nano-enabled devices from research laboratories to real-world adoption.

36 MATERIALS SCIENCE↗

Nature‐Inspired Emerging Chiral Liquid Crystal Nanostructures: From Molecular Self‐Assembly to DNA Mesophase and Nanocolloids

Abstract Liquid crystals (LCs) are omnipresent in living matter, whose chirality is an elegant and distinct feature in certain plant tissues, the cuticles of crabs, beetles, arthropods, and beyond. Taking inspiration from nature, researchers have recently devoted extensive efforts toward developing chiral liquid crystalline materials with self‐organized nanostructures and exploring their potential applications in diverse fields ranging from dynamic photonics to energy and safety issues. In this review, an account on the state of the art of emerging chiral liquid crystalline nanostructured materials and their technological applications is provided. First, an overview on the significance of chiral liquid crystalline architectures in various living systems is given. Then, the recent significant progress in different chiral liquid crystalline systems including thermotropic LCs (cholesteric LCs, cubic blue phases, achiral bent‐core LCs, etc.) and lyotropic LCs (DNA LCs, nanocellulose LCs, and graphene oxide LCs) is showcased. The review concludes with a perspective on the future scope, opportunities, and challenges in these truly advanced functional soft materials and their promising applications.

Wang, Ling↗

Synthesis of 2H/ fcc -Heterophase AuCu Nanostructures for Highly Efficient Electrochemical CO 2 Reduction at Industrial Current Densities

Structural engineering of nanomaterials offers a promising way for developing high-performance catalysts toward catalysis. However, the delicate modulation of thermodynamically unfavorable nanostructures with unconventional phases still remains a challenge. Here, in this study, the synthesis of hierarchical AuCu nanostructures is reported with hexagonal close-packed (2H-type)/face-centered cubic (fcc) heterophase, high-index facets, planar defects (e.g., stacking faults, twin boundaries, and grain boundaries), and tunable Cu content. The obtained 2H/fcc Au 99 Cu 1 hierarchical nanosheets exhibit excellent performance for the electrocatalytic CO 2 reduction to produce CO, outperforming the 2H/fcc Au 91 Cu 9 and fcc Au 99 Cu 1 . The experimental results, especially those obtained by in-situ differential electrochemical mass spectroscopy and attenuated total reflection Fourier-transform infrared spectroscopy, suggest that the enhanced catalytic performance of 2H/fcc Au 99 Cu 1 arises from the unconventional 2H/fcc heterophase, high-index facets, planar defects, and appropriate alloying of Cu. Impressively, the 2H/fcc Au 99 Cu 1 shows CO Faradaic efficiencies of 96.6% and 92.6% at industrial current densities of 300 and 500 mA cm -2 , respectively, as well as good durability, placing it among the best CO 2 reduction electrocatalysts for CO production. The atomically structural regulation based on phase engineering of nanomaterials (PEN) provides an avenue for the rational design and preparation of high-performance electrocatalysts for various catalytic applications.

36 MATERIALS SCIENCE↗

Dual‐Scale Nanostructures via Evaporative Assembly

Abstract Dual‐scale hierarchical structures with regular microscale patterns and varying degree of nanoscale crystalline order are synthesized on physically and chemically homogeneous substrates by evaporative self‐assembly with a suspension of DNA‐functionalized nanoparticles (NPs) with a charged core shell. For a certain NP concentration range, periodic concentric rings in a stripe‐like micropattern are produced over macroscale surface areas by an NP monolayer with hexagonal lattice structure at the nanoscale. The stripe width, spacing, and nanoparticle ordering can be controlled by varying the NP concentration. The results indicate that the interplay between “stick‐slip” motion of the droplet contact line and coulombic and steric NP interactions control the formation of the observed structures. A simple analytical model is proposed to account for the experimental observations and guide the future design of different nanostructure morphologies. This work demonstrates a simple cost‐effective mask‐free method for fabricating large‐area nanostructured 2D materials and metasurfaces for applications ranging from energy conversion/storage to optoelectronics and nanophotonics.

Srivastava, Sunita↗

Oxidation Driven Thin‐Film Solid‐State Metal Dealloying Forming Bicontinuous Nanostructures

Abstract Solid‐state metal dealloying (SSMD) is a promising method for fabricating nanoscale metallic composites and nanoporous metals across a range of materials. Thin‐film SSMD is particularly attractive due to its ability to create fine features via solid‐state interfacial reactions within a thin‐film geometry, which can be integrated into devices for various applications. This work examines a new dealloying couple, namely the Nb–Al alloy with the dealloying agent Sc, as previously predicted in the machine‐learning (ML) models. Prior ML predictions aimed to guide the design of nanoarchitectured materials through dealloying, relying on intuition‐driven discovery within a large parameter space. However, this work reveals that at the nanoscale, the involvement of oxygen in thin film processing may instead drive the dealloying process, resulting in the formation of bicontinuous nanostructures similar to those formed by metal‐agent dealloying. The phase evolution, as well as chemical and morphological changes, are closely analyzed using a combination of X‐ray absorption spectroscopy, diffraction, and scanning transmission electron microscopy to understand the mechanisms behind nanostructure formation. The findings suggest a potential pathway for utilizing oxygen to drive the formation of bicontinuous metal–metal oxide nanocomposites, paving the way for further development of functional nanoporous materials in diverse fields.

36 MATERIALS SCIENCE↗

Creating Zipper‐Like van der Waals Gap Discontinuity in Low‐Temperature‐Processed Nanostructured PbBi 2 n Te 1+3 n : Enhanced Phonon Scattering and Improved Thermoelectric Performance

Abstract Nanoengineered materials can embody distinct atomic structures which deviate from that of the bulk‐grain counterpart and induce significantly modified electronic structures and physical/chemical properties. The phonon structure and thermal properties, which can also be potentially modulated by the modified atomic structure in nanostructured materials, however, are seldom investigated. Employed here is a mild approach to fabricate nanostructured PbBi 2 n Te 1+3 n using a solution‐synthesized PbTe‐Bi 2 Te 3 nano‐heterostructure as a precursor. The as‐obtained monoliths have unprecedented atomic structure, differing from that of the bulk counterpart, especially the zipper‐like van der Waals gap discontinuity and the random arrangement of septuple‐quintuple layers. These structural motifs break the lattice periodicity and coherence of phonon transport, leading to ultralow thermal conductivity and excellent thermoelectric z T .

Xu, Biao↗