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At least 361 records · Page 20

Unusual electrical conductivity driven by localized stoichiometry modification at vertical epitaxial interfaces

Precise control of lattice mismatch accommodation and interfacial cation diffusion is critical to modulate correlated functionalities in epitaxial heterostructures, particularly when the interface composition is positioned near a compositional phase transition boundary. Here we select La 1-x Sr x MnO 3 (LSMO) as a prototype phase transition oxide and establish vertical epitaxial interfaces with NiO for exploring the strong interplay between strain accommodation, stoichiometry modification, and localized electron transport across the interface. It is found that localized stoichiometry modification overcomes the dead layer problem plaguing LSMO and leads to strongly directional conductivity, as manifested by a more than three orders of magnitude difference between out-of-plane and in-plane conductivity. Comprehensive atomic scale structural characterization and transport measurements reveal that this emerging behavior is created by a compositional change produced by preferential cation diffusion that pushes the LSMO phase transition from insulating into metallic within an ultrathin interface region. This study explores the nature of unusual electrical conductivity at vertical epitaxial interfaces and highlights the beneficial role of controllable cation diffusion that enables emerging functionalities for a broad range of potential applications such as memristors, spintronic devices, and novel nanoelectronic devices using strongly correlated materials.

36 MATERIALS SCIENCE↗

Post-polymerization modification of polymethacrylates enabled by keto–enol tautomerization

We report a post-polymerization modification strategy to functionalize methacrylic copolymers through enol-ester transesterification. A new monomer, vinyl methacryloxy acetate (VMAc), containing both enol-ester and methacryloyl functionality, was successfully copolymerized with methyl methacrylate (MMA) by selective reversible addition–fragmentation chain transfer (RAFT) polymerization. Post-polymerization modification of pendent enol esters proceeded through an “irreversible” transesterification process, driven by the low nucleophilicity of the tautomerization product, to result in high conversion under mild conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enabling electrochemical N 2 reduction to NH 3 in the low overpotential region using non-noble metal Bi electrodes via surface composition modification

The electrochemical N 2 reduction reaction (ENRR) that can produce NH 3 using water as the hydrogen source at ambient temperature and pressure can be an exciting alternative to the Haber–Bosch process. The major challenge for electrochemical NH 3 production is the competing hydrogen evolution reaction (HER), which seriously limits the faradaic efficiency (FE) for NH 3 production. To date, noble metal electrocatalysts that are inactive for the HER have mainly been investigated for the ENRR. Studies reporting a FE greater than 10% for NH 3 production using non-noble metal catalysts in the low overpotential region (E ≤ 0.2 V vs. RHE) are very rare. This study reports effective electrochemical surface modification strategies that drastically increase the ENRR activity of a non-noble Bi electrode in the low overpotential region and achieve a FE for NH 3 production as high as 13.2% at -0.2 V vs. RHE in pH 7.5 phosphate buffer. Finally, the effect of each of the surface modifications on the activity for the ENRR and the electrode stability during the ENRR were systematically elucidated, which may be used to develop general strategies to enhance the ENRR activities of other non-noble metal electrodes in the low overpotential region.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced charge carrier extraction and transport with interface modification for efficient tin-based perovskite solar cells

Interface modification improves charge carrier extraction in tin-based perovskite solar cells. Tin-based perovskites have become the most promising non-lead perovskites due to their ideal band gap and low toxicity. Although the open circuit voltage of tin-based perovskite solar cells (TPSCs) continues to approach the theoretical value, the short-circuit current is still far from the theoretical value. Here, we describe an interface modification method by regulating the property of hole transport layer, PEDOT:PSS, which improves the surface molecular morphology and the energy level alignment of PEDOT:PSS/perovskite interface. Advanced GIWAXS and IR s-SNOM characterization are conducted to achieve multi-dimensional characterization of nanoscale surface morphology and chemical distribution of PEDOT:PSS. With the multi-attribute optimization, charge carrier extraction and non-radiative recombination are also improved. The resultant TPSCs exhibit a higher power conversion efficiency of 13.32% in compared with the control device of 10.50%, accompanied with an increase in the short-circuit current from 18.10 to 20.50 mA cm −2 and FF from 68.23% to 76.43%. This work demonstrates a reliable strategy for improving charge carrier extraction and device performance for lead-free TPSCs.

Zhao, Zhenzhu↗

Support modification by phosphonic acid ligands controls ethylene hydroformylation on single-atom rhodium sites

To investigate the ability of surface-bound ligands to control activity toward ethylene hydroformylation, we modified site-isolated Rh 1 /TiO 2 with a series of substituted benzyl phosphonic acids. We found that modification of the support by phosphonic acids reduced break-in times for hydroformylation by 4× and increased absolute hydroformylation activity by up to 18× compared to unmodified catalyst at 150 °C. All functionalized catalysts improved hydroformylation activity by at least 9× and improved selectivity by between 7× and 60× relative to the unmodified catalyst. Carbon monoxide probe–molecule spectroscopy indicated that the enhancements in activity among modified samples were due to changes in the local environment of the active Rh site. Specifically, the bite angle of adsorbed carbon monoxide, as determined from infrared spectra, correlated with hydroformylation activity. These findings demonstrate that Rh 1 active sites are highly sensitive to modification of the support with organic ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Organo-catalyzed deamination of polystyrene sulfonamide for diverse post-polymerization modification of styrenic polymers

Post-polymerization modification allows for the incorporation of functional groups that would otherwise be incompatible with polymerization conditions, enhancing synthetic efficiency and facilitating the creation of complex polymer architectures for specialized applications, such as biomedical devices, electronics, and advanced coatings. Herein, we report a method inspired by late-stage functionalization of small molecules for the post-polymerization modification of aromatic polymers, specifically polystyrene (PS), under mild reaction conditions. First, PS was converted to polystyrene sulfonamide (PSSNH 2 ) with an 85% yield using established procedures. PSSNH 2 was subsequently transformed into a reactive sulfinate by deamination using an N-heterocyclic carbene (NHC) catalyst and benzaldehyde. The catalytic process was optimized by varying catalysts, solvents, bases, temperatures, and reaction times. The highest degree of deamination was 88% with a bicyclic NHC and K 2 CO 3 base in DMSO for 18 hours at 120 °C. The reactive sulfinate was then treated with various functional reagents, resulting in a library of aromatic polymers with different substituents with high degrees of functionalization ranging from 74% to 98%. Similarly, we modified expanded PS waste with trifluorobutyl iodide with a degree of functionalization of 72%, highlighting a new avenue for plastic upgrading. This approach could be used to rapidly generate functionalized polymers from PS with potential applications, including antibacterial properties and flame retardancy.

Shrestha, Tulaja [Univ. of Delaware, Newark, DE (U↗

Enhancement of the magnetic interfacial exchange energy at a specific interface in NiFe/CoO/Co trilayer thin films via ion-beam modification

A series of ferromagnetic Ni{sub 80}Fe{sub 20}(55 nm)/antiferromagnetic CoO (25 to 200 nm)/ferromagnetic Co (55 nm)/SiO{sub 2}(substrate) trilayer thin films were fabricated by ion-beam assisted deposition in order to understand the role of ion beam modification on the interfacial and interlayer coupling. The microstructural study using transmission electron microscopy, X-ray reflectometry, and polarised neutron reflectometry showed that ion-beam modification during the deposition process led to an oxygen-rich Co/CoO nanocomposite interface region at the bottom layer. This interface caused a high exchange bias field for the ferromagnetic cobalt. However, the exchange bias for top permalloy ferromagnet remained low, in line with expectations from the literature for the typical interfacial energy. This suggest that the ion-beam enhancement of the magnetic exchange bias is localized to the Co/CoO interface where local microstructural effects provide the dominant mechanism.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Two-dimensional nanostructured Y{sub 2}O{sub 3} particles for viscosity modification

Nanoparticle additives have been shown to improve the mechanical and transport phenomena of various liquids; however, little has been done to try and explain the rheological modifications provided from such modifications from a theoretical standpoint. Here, we report a non-Einstein-like reduction of viscosity of mineral oil with the utilization of yttrium oxide nanosheet additives. Experimental results, coupled with generalized smoothed-particle hydrodynamics simulations, provide insight into the mechanism behind this reduction of fluid shear stress. The ordered inclination of these two-dimensional nanoparticle additives markedly improves the lubricating properties of the mineral oil, ultimately reducing the friction, and providing a way in designing and understanding next generation of lubricants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of surface modification in atomic force microscope-induced nanolithography of oxygen deficient La{sub 0.67}Ba{sub 0.33}MnO{sub 3−δ} thin films

We report our studies of the nanolithographic surface modifications induced by an Atomic Force Microscope (AFM) in epitaxial thin films of oxygen deficient Lanthanum Barium Manganese Oxide (La{sub 0.67}Ba{sub 0.33}MnO{sub 3−δ}). The pattern characteristics depend on the tip voltage, tip polarity, voltage duration, tip force, and humidity. We have used Electron Energy Dispersive X-Ray Spectroscopy (EDS) to analyze the chemical changes associated with the surface modifications produced with a negatively biased AFM tip. A significant increase in the oxygen stoichiometry for the patterned regions relative to the pristine film surface is observed. The results also indicate changes in the cation stoichiometry, specifically a decrease in the Lanthanum and Manganese concentrations and an increase in the Barium concentration in the patterned regions.

36 MATERIALS SCIENCE↗

Modification of modulated plasma plumes for the quasi-phase-matching of high-order harmonics in different spectral ranges

We demonstrate the technique allowing the fine tuning of the distance between the laser-produced plasma plumes on the surfaces of different materials, as well as the variation of the sizes of these plumes. The modification of plasma formations is based on the tilting of the multi-slit mask placed between the heating laser beam and target surface, as well as the positioning of this mask in the telescope placed on the path of heating radiation. The modulated plasma plumes with the sizes of single plume ranging between 0.1 and 1 mm were produced on the manganese and silver targets. Modification of the geometrical parameters of plasma plumes proved to be useful for the fine tuning of the quasi-phase-matched high-order harmonics generated in such structures during propagation of the ultrashort laser pulses. We show the enhancement of some groups of harmonics along the plateau range and the tuning of maximally enhanced harmonic by variable modulation of the plasma.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Surface modifications with Lissajous trajectories using atomic force microscopy

In this paper, we report a method for atomic force microscopy surface modifications with single-tone and multiple-resolution Lissajous trajectories. The tip mechanical scratching experiments with two series of Lissajous trajectories were carried out on monolayer films. The scratching processes with two scan methods have been illustrated. As an application, the tip-based triboelectrification phenomenon on the silicon dioxide surface with Lissajous trajectories was investigated. The triboelectric charges generated within the tip rubbed area on the surface were characterized in-situ by scanning Kelvin force microscopy. This method would provide a promising and cost-effective approach for surface modifications and nanofabrication.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Surface modification of ferritic steels using MEVVA and duoplasmatron ion sources

Metal Vapor Vacuum Arc (MEVVA) ion source (IS) is a unique tool for production of high intensity metal ion beam that can be used for material surface modification. From the other hand, the duoplasmatron ion source provides the high intensity gas ion beams. The MEVVA and duoplasmatron IS developed in Institute for Theoretical and Experimental Physics were used for the reactor steel surface modification experiments. Response of ferritic-martensitic steel specimens on titanium and nitrogen ions implantation and consequent vacuum annealing was investigated. Increase in microhardness of near surface region of irradiated specimens was observed. Local chemical analysis shows atom mixing and redistribution in the implanted layer followed with formation of ultrafine precipitates after annealing.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Two-chamber configuration of Bio-Nano electron cyclotron resonance ion source for fullerene modification

We report on the modification of fullerenes with iron and chlorine using two individually controllable plasmas in the Bio-Nano electron cyclotron resonance ion source (ECRIS). One of the plasmas is composed of fullerene and the other one is composed of iron and chlorine. The online ion beam analysis allows one to investigate the rate of the vapor-phase collisional modification process in the ECRIS, while the offline analyses (e.g., liquid chromatography-mass spectrometry) of the materials deposited on the plasma chamber can give information on the surface-type process. Both analytical methods show the presence of modified fullerenes such as fullerene-chlorine, fullerene-iron, and fullerene-chlorine-iron.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Modification of electron states in CdTe absorber due to a buffer layer in CdTe/CdS solar cells

By application of the ac admittance spectroscopy method, the defect state energy distributions were determined in CdTe incorporated in thin film solar cell structures concluded on ZnO, ZnSe, and ZnS buffer layers. Together with the Mott-Schottky analysis, the results revealed a strong modification of the defect density of states and the concentration of the uncompensated acceptors as influenced by the choice of the buffer layer. In the solar cells formed on ZnSe and ZnS, the Fermi level and the energy position of the dominant deep trap levels were observed to shift closer to the midgap of CdTe, suggesting the mid-gap states may act as recombination centers and impact the open-circuit voltage and the fill factor of the solar cells. For the deeper states, the broadening parameter was observed to increase, indicating fluctuations of the charge on a microscopic scale. Such changes can be attributed to the grain-boundary strain and the modification of the charge trapped at the grain-boundary interface states in polycrystalline CdTe.

36 MATERIALS SCIENCE↗

Modification to the accelerator of the NBI-1B ion source for improving the injection efficiency

Minimizing power loss of a neutral beam imposes modification of the accelerator of the ion source for further improvement of the beam optics. The beam optics can be improved by focusing beamlets. The injection efficiencies by the steering of ion beamlets are investigated numerically to find the optimum modification of the accelerator design of the NBI-1B ion source. The beam power loss was reduced by aperture displacement of three edge beamlets arrays considering power loadings on the beamline components. Successful testing and operation of the ion source at 60 keV/84% of injection efficiency led to the possibility of enhancing the system capability to a 2.4 MW power level at 100 keV/1.9 μP.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

A new setup for the investigation of swift heavy ion induced particle emission and surface modifications

The irradiation with fast ions with kinetic energies of >10 MeV leads to the deposition of a high amount of energy along their trajectory (up to several ten keV/nm). The energy is mainly transferred to the electronic subsystem and induces different secondary processes of excitations, which result in significant material modifications. A new setup to study these ion induced effects on surfaces will be described in this paper. The setup combines a variable irradiation chamber with different techniques of surface characterizations like scanning probe microscopy, time-of-flight secondary ion, and neutral mass spectrometry, as well as low energy electron diffraction under ultra high vacuum conditions, and is mounted at a beamline of the universal linear accelerator (UNILAC) of the GSI facility in Darmstadt, Germany. Here, samples can be irradiated with high-energy ions with a total kinetic energy up to several GeVs under different angles of incidence. Our setup enables the preparation and in situ analysis of different types of sample systems ranging from metals to insulators. Time-of-flight secondary ion mass spectrometry enables us to study the chemical composition of the surface, while scanning probe microscopy allows a detailed view into the local electrical and morphological conditions of the sample surface down to atomic scales. With the new setup, particle emission during irradiation as well as persistent modifications of the surface after irradiation can thus be studied. We present first data obtained with the new setup, including a novel measuring protocol for time-of-flight mass spectrometry with the GSI UNILAC accelerator.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Large modification in insulator-metal transition of VO{sub 2} films grown on Al{sub 2}O{sub 3} (001) by high energy ion irradiation in biased reactive sputtering

High energy ion irradiation in biased reactive sputtering enabled significant modification of insulator-metal transition (IMT) properties of VO{sub 2} films grown on Al{sub 2}O{sub 3} (001). Even at a high biasing voltage with mean ion energy of around 325 eV induced by the rf substrate biasing power of 40 W, VO{sub 2} film revealed low IMT temperature (T{sub IMT}) at 309 K (36 °C) together with nearly two orders magnitude of resistance change. Raman measurements from −193 °C evidenced that the monoclinic VO{sub 2} lattice begins to transform to rutile-tetragonal lattice near room temperature. Raman spectra showed the in-plane compressive stress in biased VO{sub 2} films, which results in shortening of V–V distance along a-axis of monoclinic structure, a{sub M}-axis (c{sub R}-axis) and thus lowering the T{sub IMT}. In respect to that matter, significant effects in shortening the in-plane axis were observed through transmission electron microscopy observations. V2p{sub 3/2} spectra from XPS measurements suggested that high energy ion irradiation also induced oxygen vacancies and resulted for an early transition onset and rather broader transition properties. Earlier band gap closing against the temperature in VO{sub 2} film with higher biasing power was also probed by ultraviolet photoelectron spectroscopy. Present results with significant modification of IMT behavior of films deposited at high-energy ion irradiation with T{sub IMT} near the room temperature could be a newly and effective approach to both exploring mechanisms of IMT and further applications of this material, due to the fixed deposition conditions and rather thicker VO{sub 2} films.

36 MATERIALS SCIENCE↗

Active control of resistive wall mode via modification of external tearing index

Modification of the external tearing index, Δ ext ′ , by magnetic feedback is analytically investigated for the purpose of controlling the resistive plasma resistive wall mode (RP-RWM). The matching method is pursued by deriving expressions for the close-loop Δ ext ′ and by linking it to the counterpart from the inner layer. Various feedback coil configurations are found to generally reduce Δ ext ′ and stabilize the RWM, with either proportional or derivative control. Feedback modification of Δ ext ′ is found to be generally independent of the inner layer resistive interchange index D R , confirming that feedback action primarily modifies the solution in the outer ideal region for the RP-RWM. Exception occurs when either the inner layer favorable curvature effect becomes sufficiently large or the feedback action is sufficiently strong to introduce a rotating RP-RWM in the static plasma, leading to complex-valued close-loop Δ ext ′ . The perturbed magnetic energy dissipation in the outer region, associated with the eddy current in the resistive wall, is identified as the key physics reason for feedback induced complex Δ ext ′ . Similar results are also obtained for active control of the external kink instability, whose open-loop growth rate is significantly reduced by inclusion of the plasma resistivity. Within the single poloidal harmonic approximation, which is most suitable for the matching approach, external active coils combined with poloidal sensors are often found to be more efficient for feedback stabilization of the mode at large proportional gain values. This counter-intuitive result is explained as the lack of (non-resonant) poloidal harmonics for proper description of the feedback coil geometry.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗