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At least 523 records · Page 29

Solvation directed morphological control in metal oxide nanostructures

The development of structural hierarchy on various length scales during the crystallization process is ubiquitous in biological systems and minerals and is common in synthetic nanomaterials. The driving forces for the formation of complex architectures range from local interfacial interactions, that modify interfacial speciation, local supersaturation, and nucleation barriers, to macroscopic interparticle forces. Although it is enticing to interpret the formation of hierarchical architectures as the assembly of independently nucleated building blocks, crystallization pathways often follow monomer-by-monomer addition with structural complexity arising from interfacial chemical coupling and strongly correlated fluctuation dynamics in the electric double layers. Here, we show that the development of structural hierarchy through heterogeneous nucleation is driven by dipolar and solvation forces. Specifically, coupled simulations and experimental studies revealed that dipole build-up along the slow growth direction can trigger twinning and the development of branched architectures. Enthalpic solvation interactions were shown to either enhance or reduce the dipole moment of the nanoparticles and, thereby, control crystal morphology and architecture. The systematic studies of chemical coupling between different solvents and undercoordinated surface atoms of the growing nanocrystals revealed the mechanism of dimensionality control and the development of structural hierarchy without ligands or structure-directing agents.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Study of the water dynamics near hydrophilic, nanostructured CuO surfaces by quasielastic and inelastic neutron scattering

We have used quasielastic and inelastic neutron scattering to investigate the structure, dynamics, and phase transitions of water interacting with superhydrophilic CuO surfaces that not only possess a strong affinity for water but also a “grass-like” topography that is rough on both micro- and nanoscales. Here, we report quasielastic neutron scattering (QENS) measurements on two samples differing in water content at five temperatures below 280 K. The QENS spectra show water undergoing two different types of diffusive motion near the CuO surfaces: a “slow” translational diffusion occurring on a nanosecond time scale and a faster rotational motion. Further from the surfaces, there is “fast” translational diffusion comparable in rate to that of bulk supercooled water and the rotational motion occurring in the interfacial water. Analysis of the QENS spectra supports wetting of water to the CuO blades as seen in electron microscopy images. In addition, we observe an anomalous temperature dependence of the QENS spectra on cooling from 270 to 230 K with features consistent with a liquid–liquid phase transition. We suggest that the solvent-like properties of the coexisting bulk-like water in our CuO samples are a significant factor in determining the temperature dependence of the interfacial water’s dynamics. Our results are compared with those obtained from two well-studied substrate classes: (1) silicas that contain ordered cylindrical nanopores but have weaker hydrophilicity and (2) nanoparticles of other transition-metal oxides, such as TiO 2 , which share the strong hydrophilicity of our samples but lack their porosity.

36 MATERIALS SCIENCE↗

Voltage-induced modulation of interfacial ionic liquids measured using surface plasmon resonant grating nanostructures

We have used surface plasmon resonant metal gratings to induce and probe the dielectric response (i.e., electro-optic modulation) of ionic liquids (ILs) at electrode interfaces. Here, the cross-plane electric field at the electrode surface modulates the refractive index of the IL due to the Pockels effect. This is observed as a shift in the resonant angle of the grating (i.e., Δϕ), which can be related to the change in the local index of refraction of the electrolyte (i.e., Δnlocal). The reflection modulation of the IL is compared against a polar (D2O) and a non-polar solvent (benzene) to confirm the electro-optic origin of resonance shift. The electrostatic accumulation of ions from the IL induces local index changes to the gratings over the extent of electrical double layer (EDL) thickness. Finite difference time domain simulations are used to relate the observed shifts in the plasmon resonance and change in reflection to the change in the local index of refraction of the electrolyte and the thickness of the EDL. Simultaneously using the wavelength and intensity shift of the resonance enables us to determine both the effective thickness and Δn of the double layer. We believe that this technique can be used more broadly, allowing the dynamics associated with the potential-induced ordering and rearrangement of ionic species in electrode–solution interfaces.

Chemistry↗

A MEMS dynamic mechanical analyzer for in situ viscoelastic characterization of 3D printed nanostructures

Cellular metamaterial structures with sub-micron features have shown the ability to become excellent energy absorbing materials for impact mitigation due to the enhanced mechanical properties of materials at the nanoscale. However, in order to optimize the design of these energy absorbing metamaterial structures we need to be able to measure the dynamic properties of the sub-micron features such as storage and loss moduli and the loss factor. Therefore, at scale testing is required to capture the scale, temperature, and strain rate dependent material properties of these nanoscale materials. This study presents the design, fabrication, and calibration of a MEMS-based dynamic mechanical analyzer (DMA) that can be directly integrated with the two photon lithography (TPL) process commonly used to fabricate metamaterial structures with nanoscale features. The MEMS-based DMA consists of a chevron style thermal actuator used to generate a tensile load on the structure and two differential capacitive sensors on each side of the structure used to measure load and displacement. This design demonstrated 1.5 ± 0.75 nm displacement resolution and 104 ± 52 nN load resolution, respectively. Dynamic mechanical analysis was successfully conducted on a single nanowire feature printed between the load and displacement stages of the MEMS device with testing frequencies ranging between 0.01–10 Hz and testing temperatures ranging between 22 °C–47 °C. These initial tests on an exemplar TPL part demonstrate that the printed nanowire behaves as a viscoelastic material wherein the transition from glassy to viscous behavior has already set in at the room temperature.

42 ENGINEERING↗

Aerotaxy: gas-phase epitaxy of quasi 1D nanostructures

Cost- and resource-efficient growth is necessary for many applications of semiconductor nanowires. We here present the design, operational details and theory behind Aerotaxy, a scalable alternative technology for producing quality crystalline nanowires at a remarkably high growth rate and throughput. Using size-controlled Au seed particles and organometallic precursors, Aerotaxy can produce nanowires with perfect crystallinity and controllable dimensions, and the method is suitable to meet industrial production requirements. Here, we explain why Aerotaxy is an efficient method for fabricating semiconductor nanowires and explain the technical aspects of our custom-built Aerotaxy system. Investigations using SEM (Scanning Electron Microscope), TEM (Transmission Electron Microscope)and other characterization methods are used to support the claim that Aerotaxy is indeed a scalable method capable of producing nanowires with reproducible properties. We have investigated both binary and ternary III–V semiconductor material systems like GaAs and GaAsP. In addition, common aspects of Aerotaxy nanowires deduced from experimental observations are used to validate the Aerotaxy growth model, based on a computational flow dynamics (CFD) approach. We compare the experimental results with the model behaviour to better understand Aerotaxy growth.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Edge states of α-bismuthene nanostructures

We present a systematic investigation of the edge states (ESs) of two-dimensional α-bismuthene (α-Bi) structures self-assembled on highly oriented pyrolytic graphite substrates, using scanning tunnelling microscopy and scanning tunnelling spectroscopy. The measurements are carried out for 3ML, 5ML and 7ML thick Bi structures. Our spectroscopy studies reveal clear features at the edges of the 5ML and 7ML thick structures, and the positions of the ESs coincide with the topographical step edges. In contrast, in 3ML structures the ESs appear to be absent and instead new states are sometimes observed, far from the topographical edge. These states are associated with a moiré pattern and result from strain-induced modulation of the topology. Our observations demonstrate the impact on the ESs of coupling to adjacent structures.

2D materials↗

Near-field-driven radiative thermal dynamics in aperiodic photonic nanostructures

Harnessing structural correlations in near-field plasmonic and polaritonic systems hold untapped potential for controlling light–matter interactions at the nanoscale. By tuning these correlations, one can reshape mode localization, coupling, and spectral distribution which are properties central to manipulating energy transport and field enhancement in nanophotonic platforms. We exploit Vogel spirals, an aperiodic geometry where a single parameter dictates spatial correlations, to show how correlation strength reshapes the modal spectrum and transient dynamics of near-field coupling. As a proof of concept, we demonstrate that aperiodic configurations outperform both uncorrelated (random) and periodic arrays in controlling near-field radiative heat-transfer dynamics. These results establish deterministic aperiodic order as a powerful platform for tailoring correlated electromagnetic responses in next-generation nanophotonic devices.

36 MATERIALS SCIENCE↗

Nanostructured $\mathrm{GaAs/(Al,Ga)As}$ Waveguide for Low-Density Polariton Condensation from a Bound State in the Continuum

Exciton-polaritons are hybrid light-matter states that arise from strong coupling between an exciton resonance and a photonic cavity mode. As bosonic excitations, they can undergo a phase transition to a condensed state that can emit coherent light without a population inversion. This aspect makes them good candidates for thresholdless lasers, yet short exciton-polariton lifetime has made it difficult to achieve condensation at very low power densities. In this sense, long-lived symmetry-protected states are excellent candidates to overcome the limitations that arise from the finite mirror reflectivity of monolithic microcavities. In this work we use a photonic symmetry-protected bound state in the continuum coupled to an excitonic resonance to achieve state-of-the-art polariton condensation threshold in a GaAs/(Al,Ga)As waveguide. Most important, we show the influence of fabrication control and how surface passivation via atomic layer deposition provides a way to reduce exciton quenching at the grating sidewalls.

74 ATOMIC AND MOLECULAR PHYSICS↗

Towards scanning nanostructure X-ray microscopy

This article demonstrates spatial mapping of the local and nanoscale structure of thin film objects using spatially resolved pair distribution function (PDF) analysis of synchrotron X-ray diffraction data. This is exemplified in a lab-on-chip combinatorial array of sample spots containing catalytically interesting nanoparticles deposited from liquid precursors using an ink-jet liquid-handling system. A software implementation is presented of the whole protocol, including an approach for automated data acquisition and analysis using the atomic PDF method. The protocol software can handle semi-automated data reduction, normalization and modeling, with user-defined recipes generating a comprehensive collection of metadata and analysis results. By slicing the collection using included functions, it is possible to build images of different contrast features chosen by the user, giving insights into different aspects of the local structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Hybrid Nanostructured Ni(OH) 2 /NiO for High Capacity Lithium–ion Battery Anodes

A straightforward hydrothermal process followed by a controlled calcination technique is introduced for the synthesis of a Ni(OH) 2 modified NiO nanohybrid structure. Conversion materials as Li-ion battery anodes, NiO in this case, suffer from capacity fade and structural/morphological instability during lithiation and delithiation. The novelty of this work is in utilizing this hybrid configuration to increase the specific capacity and enable reversible electrochemistry. Here, we study the lithiation/delithiation process of NiO using a suite of spectroscopy and microscopy techniques from the atomic to electrode scale. We propose a mechanism for a reversible redox couple behavior of the NiO electrode by means of a hybrid Ni(OH)2/NiO structure. The ultimate objective of this work is to guide the development of anode with rationally-designed heterogeneity to create high capacity Li-ion batteries with excellent cycling and rate performance.

25 ENERGY STORAGE↗

Discovering polyelemental nanostructures with redistributed plasmonic modes through combinatorial synthesis

Coupling plasmonic and functional materials provides a promising way to generate multifunctional structures. However, finding plasmonic nanomaterials and elucidating the roles of various geometric and dielectric configurations are tedious. This work describes a combinatorial approach to rapidly exploring and identifying plasmonic heteronanomaterials. Symmetry-broken noble/non-noble metal particle heterojunctions (~100 nanometers) were synthesized on multiwindow silicon chips with silicon nitride membranes. The metal types and the interface locations were controlled to establish a nanoparticle library, where the particle morphology and scattering color can be rapidly screened. By correlating structural data with near- and far-field single-particle spectroscopy data, we found that certain low-energy plasmonic modes could be supported across the heterointerface, while others are localized. Furthermore, we found a series of triangular heteronanoplates stabilized by epitaxial Moiré superlattices, which show strong plasmonic responses despite largely comprising a lossy metal (~70 atomic %). These architectures can become the basis for multifunctional and cost-effective plasmonic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Revealing the Nanostructure of Mesoporous Fuel Cell Catalyst Supports for Durable, High-Power Performance

Achieving high power performance and durability with low Pt loadings are critical challenges for proton exchange membrane fuel cells. PtCo catalysts developed on new carbon black supports show promise by simultaneously providing good oxygen reduction kinetics and local oxygen transport. We investigate the role of nanoscale morphology in the performance of these catalysts supported on accessible (HSC-e and HSC-f) and conventional (Ketjen Black) porous carbons using 3D electron tomography, nitrogen sorption, and electrochemical performance measurements. We find that the accessible porous carbons have hollow interiors with mesopores that are larger and more numerous than conventional porous carbons. However, mesopore-sized openings (>2 nm width) are too rare to account for significant oxygen transport. Instead we propose the primary oxygen transport pathway into the interior is through 1–2 nm microporous channels permeating the carbon. The increased mesoporosity in the accessible porous carbons results in a shorter diffusion pathlength through constrictive, tortuous micropores in the support shell leading to lower local oxygen transport resistance. In durability testing, the accessible porous carbons show faster rates of electrochemical surface area loss, likely from fewer constrictive pores that would mitigate coarsening, but maintain superior high current density performance at end of test from the improved local oxygen transport.

Electrochemistry↗

Selective Plasticization of Poly (ethylene oxide) (PEO) Block in Nanostructured Polystyrene– PEO– Polystyrene Triblock Copolymer Electrolytes

The plasticization of a polymer electrolyte usually promotes its ionic conductivity but decreases its storage modulus due to the increased polymer chain flexibility. Herein, we show that such a tradeoff between the ionic conductivity and the mechanical robustness of the polymer electrolyte can be alleviated by selective plasticization of the ion-conductive block, such as poly(ethylene oxide) (PEO) in a polystyrene (PS)– PEO–PS block copolymer (SEO) electrolyte using an ether type plasticizer, tetraethylene glycol dimethyl ether (TEGDME). In this work, at maximum plasticizer loading, the room temperature ionic conductivity increases by up to 3 orders, whereas the storage modulus, G' reduces to half, is still on the order of 10 2 MPa. At above the melting temperature of the PEO block, the dynamic storage modulus, G' of the plasticized membrane surpasses its dry PS-PEO-PS counterpart. Such a phenomenon results from that, a) TEGDME co-crystallizes with PEO to promote its crystallinity and hence the storage modulus, b) TEGDME swells the amorphous PEO phase to enhance the polymer chain segmental mobility and hence ionic conductivity, and c) the PS phase remains intact from TEGDME to keep the SEO elastic.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Emergent Nanostructure and Ion Transport in Polyzwitterion/Polyanion Blends

We investigated blends of poly(1-(3-sulfonatopropyl)-2-vinylpyridinium) (P2VPPS) and poly(lithium (trifluoromethane)sulfonimide methacrylate) (poly(MTFSI)Li) at varying molar ratios to gain a mechanistic understanding of ionic conductivity in a miscible polyzwitterion/polyanion system. This dataset contains the raw numerical data corresponding to the figures in the manuscript. The data files include the following information: (1) Experimental Data – includes X-ray and neutron scattering measurements, broadband dielectric spectroscopy (BDS) data, extracted DC conductivity values, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) results, extracted glass transition temperatures, etc. (2) CGMD Data – includes molecular dynamics (MD) trajectory files and computed structural correlations. All data files are organized/named according to the figure numbers in the manuscript.

36 MATERIALS SCIENCE↗