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At least 1,027 records · Page 57

Controlled synthesis of highly-branched plasmonic gold nanoparticles through peptoid engineering

Inspired by peptide- and protein-controlled formation of hierarchical inorganic nanostructures in nature, herein we report the design of sequence-defined peptoids for biomimetic synthesis of flower-like gold nanosuperstruc-tures. We demonstrate that the peptoid-induced morphosyn-thesis of gold nanoflowers is sequence-dependent. By varying the hydrophobicity, number of carboxylate and amino groups, and side-chain positions of peptoids, we develop a rule of thumb for designing peptoids that yield gold nanoflowers. Through a combination of hyperspectral UV-Vis absorption micro-spectroscopy (H-UVVIS-AMS) and three-photon photoemission electron microscopy (TP-PEEM), we measured the plasmonic properties of individual nanoflowers. Whereas H-UVVIS-AMS experiments revealed well-defined plasmon resonances centered at ~528 nm, TP-PEEM measurements showed an unprecedented plasmonic enhancement as high as 105 for a single nanoflower. A com-bination of the unique plasmonic property and the high sta-bility endows the peptoid-engineered nanoflowers with po-tential applications in chemical and biological imaging. FY, YC, HJ and C-LC acknowledge support by the Materials Synthesis and Simulation Across Scales (MS3) Initiative, through the Laboratory Directed Research & Development (LDRD) fund at Pacific Northwest National Laboratory (PNNL). FY was also partially supported by fellowships from Shandong Provincial Education Association for International Exchanges. YG was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. PZE acknowledges support from the Laboratory Directed Research and Development Program through a Linus Pauling Fellowship at PNNL. PNNL is multi-program national laboratory operated for the Department of Energy by Battelle under Contracts No. DE-AC05-76RL01830. The authors are most grateful to Alan Joly and Wayne Hess (PNNL) for their support with the PEEM measurements and several useful discussions.

Yan, Feng↗

Emergent properties at oxide interfaces controlled by ferroelectric polarization

Abstract Ferroelectric materials are characterized by the spontaneous polarization switchable by the applied fields, which can act as a “gate” to control various properties of ferroelectric/insulator interfaces. Here we review the recent studies on the modulation of oxide hetero-/homo-interfaces by ferroelectric polarization. We discuss the potential applications of recently developed four-dimensional scanning transmission electron microscopy and how it can provide insights into the fundamental understanding of ferroelectric polarization-induced phenomena and stimulate future computational studies. Finally, we give the outlook for the potentials, the challenges, and the opportunities for the contribution of materials computation to future progress in the area.

Chemistry↗

Controlling the polarization and vortex charge of attosecond high-harmonic beams via simultaneous spin–orbit momentum conservation

Optical interactions are governed by both spin and angular momentum conservation laws, which serve as a tool for controlling light–matter interactions or elucidating electron dynamics and structure of complex systems. Here, we uncover a form of simultaneous spin and orbital angular momentum conservation and show, theoretically and experimentally, that this phenomenon allows for unprecedented control over the divergence and polarization of extreme-ultraviolet vortex beams. High harmonics with spin and orbital angular momenta are produced, opening a novel regime of angular momentum conservation that allows for manipulation of the polarization of attosecond pulses—from linear to circular—and for the generation of circularly polarized vortices with tailored orbital angular momentum, including harmonic vortices with the same topological charge as the driving laser beam. As a result, our work paves the way to ultrafast studies of chiral systems using high-harmonic beams with designer spin and orbital angular momentum.

High-harmonic generation↗

Accessing conjugated polymers with precisely controlled heterobisfunctional chain ends via post-polymerization modification of the OTf group and controlled Pd(0)/t-Bu 3 P-catalyzed Suzuki cross-coupling polymerization

In this study, a general strategy toward the synthesis of well-defined conjugated polymers with controlled heterobisfunctional chain ends via combination of controlled Pd(0)/t-Bu 3 P Suzuki cross-coupling polymerization with the post-polymerization modification of the triflate (OTf) group was disclosed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controlling 3-D Morphology of Ni-Fe-Based Nanocatalysts for Oxygen Evolution Reaction

Controlling the 3-D morphology of nanocatalysts is one of the underexplored but important approaches for improving the sluggish kinetics of the oxygen evolution reaction (OER) in water electrolysis. This work reports a scalable, oil-based method based on thermal decomposition of organometallic complexes to yield highly uniform Ni–Fe-based nanocatalysts with a well-defined morphology (i.e. Ni–Fe core–shell, Ni/Fe alloy, and Fe–Ni core–shell). Transmission electron microscopy reveals their morphology and composition to be NiOx–FeOx/NiOx core-mixed shell, NiOx/FeOx alloy, and FeOx–NiOx core–shell. X-ray techniques resolve the electronic structures of the bulk and are supported by electron energy loss spectroscopy analysis of individual nanoparticles. These results suggest that the crystal structure of Ni is most likely to contain α-Ni(OH)2 and that the chemical environment of Fe is variable, depending on the morphology of the nanoparticle. The Ni diffusion from the amorphous Ni-based core to the iron oxide shell makes the NiOx–NiOx/FeOx core-mixed shell structure the most active and the most stable nanocatalyst, which outperforms the comparison NiOx/FeOx alloy nanoparticles expected to be active for the OER. This study suggests that the chemical environment of the mixed NiOx/FeOx alloy composition is important to achieve high electrocatalytic activity for the OER and that the 3-D morphology plays a key role in the optimization of the electrocatalytic activity and stability of the nanocatalyst for the OER.

Nanocatalysts↗

Control of focusing forces and emittances in plasma-based accelerators using near-hollow plasma channels

A near-hollow plasma channel, where the plasma density in the channel is much less than the plasma density in the walls, is proposed to provide independent control over the focusing and accelerating forces in a plasma accelerator. In this geometry the low density in the channel contributes to the focusing forces, while the accelerating fields are determined by the high density in the channel walls. The channel also provides guiding for intense laser pulses used for wakefield excitation. Both electron and positron beams can be accelerated in a nearly symmetric fashion. Near-hollow plasma channels can effectively mitigate emittance growth due to Coulomb scattering for high-energy physics applications.

43 PARTICLE ACCELERATORS↗

High carrier mobility in orientation-controlled large-grain (≥50 μm) Ge directly formed on flexible plastic by nucleation-controlled gold-induced-crystallization

High-carrier-mobility semiconductors on flexible-plastic are essential to realize flexible electronics. For this purpose, electrical properties of orientation-controlled large-grain Ge crystals on flexible-plastic directly formed by nucleation-controlled gold-induced-crystallization (GIC) are examined, and compared with those obtained by aluminum-induced-crystallization (AIC). The Ge crystals show p-type conductions. Here, hole concentrations are 2.2 × 10{sup 17} and 5.8 × 10{sup 20} cm{sup −3} for GIC-Ge and AIC-Ge, respectively, which are explained on the basis of the solubility of Au and Al in Ge. Thanks to the low hole concentration, GIC-Ge shows high hole mobility (160 cm{sup 2} V{sup −1} s{sup −1}) compared with AIC-Ge (37 cm{sup 2} V{sup −1} s{sup −1}). These demonstrate significant advantage of GIC to realize high-performance flexible-electronics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Near-infrared spectroscopy for divertor plasma diagnosis and control in DIII-D tokamak

New near infrared (NIR) spectroscopic measurements performed in the DIII-D tokamak divertor plasma suggest new viable diagnostic applications: divertor recycling and low-Z impurity flux measurements, a spectral survey for divertor Thomson scattering (DTS) diagnostic, and T{sub e} monitoring for divertor detachment control. A commercial 0.3 m spectrometer coupled to an imaging lens via optical fiber and a InGaAs 1024 pixel array detector enabled deuterium and impurity emission measurements in the range 800–2300 nm. The first full NIR survey identified D, He, B, Li, C, N, O, Ne lines and provided plasma T{sub e}, n{sub e} estimates from deuterium Paschen and Brackett series intensity and Stark line broadening analysis. The range 1.000–1.060 mm was surveyed in high-density and neon seeded divertor plasmas for spectral background emission studies for λ = 1.064 μm laser-based DTS development. The ratio of adjacent deuterium Paschen-α and Brackett Br9 lines in recombining divertor plasmas is studied for divertor T{sub e} monitoring aimed at divertor detachment real-time feedback control.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

A new apparatus design for high temperature (up to 950 °C) quasi-elastic neutron scattering in a controlled gaseous environment

A design for a sample cell system suitable for high temperature Quasi-Elastic Neutron Scattering (QENS) experiments is presented. The apparatus was developed at the Spallation Neutron Source in Oak Ridge National Lab where it is currently in use. The design provides a special sample cell environment under controlled humid or dry gas flow over a wide range of temperature up to 950 °C. Using such a cell, chemical, dynamical, and physical changes can be studied in situ under various operating conditions. While the cell combined with portable automated gas environment system is especially useful for in situ studies of microscopic dynamics under operational conditions that are similar to those of solid oxide fuel cells, it can additionally be used to study a wide variety of materials, such as high temperature proton conductors. The cell can also be used in many different neutron experiments when a suitable sample holder material is selected. The sample cell system has recently been used to reveal fast dynamic processes in quasi-elastic neutron scattering experiments, which standard probes (such as electrochemical impedance spectroscopy) could not detect. In this work, we outline the design of the sample cell system and present results demonstrating its abilities in high temperature QENS experiments.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Generation of localized strain in a thin film piezoelectric to control individual magnetoelectric heterostructures

Experimental results demonstrate the ability of a surface electrode pattern to produce sufficient in-plane strain in a PbZr0.52Ti0.48O3 (PZT) thin film clamped by a Si substrate to control magnetism in a 1000 nm diameter Ni ring. The electrode pattern and the Ni ring/PZT thin film heterostructure were designed using a finite element based micromagnetics code. The magnetoelectric heterostructures were fabricated on the PZT film using e-beam lithography and characterized using magnetic force microscopy. Application of voltage to the electrodes moved one of the “onion” state domain walls. This method enables the development of complex architectures incorporating strain-mediated multiferroic devices.

Cui, Jizhai↗

Control of excitons in multi-layer van der Waals heterostructures

We report an experimental study of excitons in a double quantum well van der Waals heterostructure made of atomically thin layers of MoS{sub 2} and hexagonal boron nitride. The emission of neutral and charged excitons is controlled by gate voltage, temperature, and both the helicity and the power of optical excitation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Understanding and control of bipolar self-doping in copper nitride

Semiconductor materials that can be doped both n-type and p-type are desirable for diode-based applications and transistor technology. Copper nitride (Cu{sub 3}N) is a metastable semiconductor with a solar-relevant bandgap that has been reported to exhibit bipolar doping behavior. However, deeper understanding and better control of the mechanism behind this behavior in Cu{sub 3}N is currently lacking in the literature. In this work, we use combinatorial growth with a temperature gradient to demonstrate both conduction types of phase-pure, sputter-deposited Cu{sub 3}N thin films. Room temperature Hall effect and Seebeck effect measurements show n-type Cu{sub 3}N with 10{sup 17} electrons/cm{sup 3} for low growth temperature (≈35 °C) and p-type with 10{sup 15} holes/cm{sup 3}–10{sup 16} holes/cm{sup 3} for elevated growth temperatures (50 °C–120 °C). Mobility for both types of Cu{sub 3}N was ≈0.1 cm{sup 2}/Vs–1 cm{sup 2}/Vs. Additionally, temperature-dependent Hall effect measurements indicate that ionized defects are an important scattering mechanism in p-type films. By combining X-ray absorption spectroscopy and first-principles defect theory, we determined that V{sub Cu} defects form preferentially in p-type Cu{sub 3}N, while Cu{sub i} defects form preferentially in n-type Cu{sub 3}N, suggesting that Cu{sub 3}N is a compensated semiconductor with conductivity type resulting from a balance between donor and acceptor defects. Based on these theoretical and experimental results, we propose a kinetic defect formation mechanism for bipolar doping in Cu{sub 3}N that is also supported by positron annihilation experiments. Overall, the results of this work highlight the importance of kinetic processes in the defect physics of metastable materials and provide a framework that can be applied when considering the properties of such materials in general.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Deformation of a super-elastic NiTiNb alloy with controllable stress hysteresis

Room temperature deformation of a Ni{sub 46.7}Ti{sub 42.8}Nb{sub 10.5} alloy was studied by in-situ synchrotron X-ray diffraction. Compared to binary NiTi alloy, the Nb dissolved in the matrix significantly increased the onset stress for Stress-Induced Martensite Transformation (SIMT). The secondary phase, effectively a Nb-nanowire dispersion in a NiTi-Nb matrix, increased the elastic stiffness of the bulk material, reduced the strain anisotropy in austenite families by load sharing during SIMT, and increased the stress hysteresis by resisting reverse phase transformation during unloading. The stress hysteresis can be controlled over a wide range by heat treatment through its influences on the residual stress of the Nb-nanowire dispersion and the stability of the austenite.

36 MATERIALS SCIENCE↗