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At least 1,243 records · Page 69

In situ nanoindentation study of plastic Co-deformation in Al-TiN nanocomposites

We performed in situ indentation in a transmission electron microscope on Al-TiN multilayers with individual layer thicknesses of 50 nm, 5 nm and 2.7 nm to explore the effect of length scales on the plastic co-deformability of a metal and a ceramic. At 50 nm, plasticity was confined to the Al layers with easy initiation of cracks in the TiN layers. At 5 nm and below, cracking in TiN was suppressed and post mortem measurements indicated a reduction in layer thickness in both layers. Our results demonstrate the profound size effect in enhancing plastic co-deformability in nanoscale metal-ceramic multilayers.

36 MATERIALS SCIENCE↗

Development of very high J c in Ba(Fe 1-x Co x ) 2 As 2 thin films grown on CaF 2

Ba(Fe 1-x Co x ) 2 As 2 is the most tunable of the Fe-based superconductors (FBS) in terms of acceptance of high densities of self-assembled and artificially introduced pinning centres which are effective in significantly increasing the critical current density, J c . Moreover, FBS are very sensitive to strain, which induces an important enhancement in critical temperature,T c , of the material. In this study we demonstrate that strain induced by the substrate can further improve J c of both single and multilayer films by more than that expected simply due to the increase in T c . The multilayer deposition of Ba(Fe 1-x Co x ) 2 As 2 on CaF 2 increases the pinning force density (F p =J c x μ₀H) by more than 60% compared to a single layer film, reaching a maximum of 84 GN/m 3 at 22.5 T and 4.2 K, the highest value ever reported in any 122 phase.

36 MATERIALS SCIENCE↗

A new method for achieving enhanced dielectric response over a wide temperature range

We report a novel approach for achieving high dielectric response over a wide temperature range. In this approach, multilayer ceramic heterostructures with constituent compositions having strategically tuned Curie points (TC) were designed and integrated with varying electrical connectivity. Interestingly, these multilayer structures exhibited different dielectric behavior in series and parallel configuration due to variations in electrical boundary conditions resulting in the differences in the strength of the electrostatic coupling. The results are explained using nonlinear thermodynamic model taking into account electrostatic interlayer interaction. We believe that present work will have huge significance in design of high performance ceramic capacitors.

36 MATERIALS SCIENCE↗

Large-Area Growth of Turbostratic Graphene on Ni(111) via Physical Vapor Deposition

Single-layer graphene has demonstrated remarkable electronic properties that are strongly influenced by interfacial bonding and break down for the lowest energy configuration of stacked graphene layers (AB Bernal). Multilayer graphene with relative rotations between carbon layers, known as turbostratic graphene, can effectively decouple the electronic states of adjacent layers, preserving properties similar to that of SLG. While the growth of AB Bernal graphene through chemical vapor deposition has been widely reported, we investigate the growth of turbostratic graphene on heteroepitaxial Ni(111) thin films utilizing physical vapor deposition. By varying the carbon deposition temperature between 800–1100°C, we report an increase in the graphene quality concomitant with a transition in the size of uniform thickness graphene, ranging from nanocrystallites to thousands of square microns. Combination Raman modes of as-grown graphene within the frequency range of 1650 cm ₋1 to 2300 cm ₋1 , along with features of the Raman 2D mode, were employed as signatures of turbostratic graphene. Bilayer and multilayer graphene were directly identified from areas that exhibited Raman characteristics of turbostratic graphene using high-resolution TEM imaging. Lastly, Raman maps of the pertinent modes reveal large regions of turbostratic graphene on Ni(111) thin films at a deposition temperature of 1100°C.

36 MATERIALS SCIENCE↗

Magnetic coupling at rare earth ferromagnet/transition metal ferromagnet interfaces: A comprehensive study of Gd/Ni

Thin film magnetic heterostructures with competing interfacial coupling and Zeeman energy provide a fertile ground to study phase transition between different equilibrium states as a function of external magnetic field and temperature. A rare-earth (RE)/transition metal (TM) ferromagnetic multilayer is a classic example where the magnetic state is determined by a competition between the Zeeman energy and antiferromagnetic interfacial exchange coupling energy. Technologically, such structures offer the possibility to engineer the macroscopic magnetic response by tuning the microscopic interactions between the layers. We have performed an exhaustive study of nickel/gadolinium as a model system for understanding RE/TM multilayers using the element-specific measurement technique x-ray magnetic circular dichroism, and determined the full magnetic state diagrams as a function of temperature and magnetic layer thickness. We compare our results to a modified Stoner-Wohlfarth-based model and provide evidence of a thickness-dependent transition to a magnetic fan state which is critical in understanding magnetoresistance effects in RE/TM systems. In conclusion, the results provide important insight for spintronics and superconducting spintronics where engineering tunable magnetic inhomogeneity is key for certain applications.

36 MATERIALS SCIENCE↗

Rapid prototyping of microchannels with surface patterns for fabrication of polymer fibers

Microfluidic technology has provided innovative solutions to numerous problems, but the cost of designing and fabricating microfluidic channels is impeding its expansion. In this study, Shrinky-Dink thermoplastic sheets are used to create multilayered complex templates for microfluidic channels. We also used inkjet and laserjet printers to raise a predetermined microchannel geometry by depositing several layers of ink for each feature consecutively. We achieved feature heights over 100 μm, which were measured and compared with surface profilometry. Templates closest to the target geometry were then used to create microfluidic devices from soft-lithography with the molds as a template. These microfluidic devices were, futhermore used to fabricate polymer microfibers using the microfluidic focusing approach to demonstrate the potential that this process has for microfluidic applications. Finally, an economic analysis was conducted to compare the price of common microfluidic template manufacturing methods. We showed that multilayer microchannels can be created significantly quicker and cheaper than current methods for design prototyping and point-of-care applications in the biomedical area.

42 ENGINEERING↗

Molecular interactions of phospholipid monolayers with a model phospholipase

The intrinsic overexpression of secretory phospholipase A2 (sPLA 2 ) in various pro-inflammatory diseases and cancers has the potential to be exploited as a therapeutic strategy for diagnostics and treatment. To explore this potential and advance our knowledge of the role of sPLA 2 in related diseases, it is necessary to systematically investigate the molecular interaction of the enzyme with lipids. By employing a Langmuir trough integrated with X-ray reflectivity and grazing incidence X-ray diffraction techniques, this study examined the molecular packing structure of 1,2-palmitoyl- sn-glycero -3-phosphocholine (DPPC) films before and after enzyme adsorption and enzyme-catalyzed degradation. Molecular interaction of sPLA 2 (from bee venom) with the DPPC monolayer exhibited Ca 2+ dependence. DPPC molecules at the interface without Ca 2+ retained a monolayer organization; upon adsorption of sPLA 2 to the monolayer the packing became tighter. In contrast, sPLA 2 -catalyzed degradation of DPPC occurred in the presence of Ca 2+ , leading to disruption of the ordered monolayer structure of DPPC. Further, the interfacial film became a mixture of highly ordered multilayer domains of palmitic acid (PA) and loosely packed monolayer phase of 1-palmitoyl-2-hydroxy- sn-glycero -3-phosphocholine (lysoPC) that potentially contained the remaining un-degraded DPPC. The redistribution of lipid degradation products into the third dimension, which produced multilayer PA domains, damaged the structural integrity of the original lipid layer and may explain the bursting of liposomes observed in other studies after a latency period of mixing liposomes with sPLA 2 . A quantitative understanding of the lipid packing and lipid-enzyme interaction provides an intuitive means of designing and optimizing lipid-related drug delivery systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Layer-by-layer assembly of a polymer of intrinsic microporosity: targeting the CO 2 /N 2 separation problem

A polymer of intrinsic microporosity, 1, has been incorporated into a series of polyelectrolyte multilayers via the layer-by-layer deposition method. One of these assemblies [a 6 nm multilayer derived from 1 plus poly(diallyldimethylammonium chloride)] showed exceptional permeation properties with respect to CO 2 and N 2 . Specifically, this film exhibited a CO 2 permeance of 130 GPU and a CO 2 /N 2 selectivity of 33.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phonon confinement and interface lattice dynamics of ultrathin high- k rare earth sesquioxide films: the case of Eu 2 O 3 on YSZ(001)

The spatial confinement of atoms at surfaces and interfaces significantly alters the lattice dynamics of thin films, heterostructures and multilayers. Ultrathin films with high dielectric constants (high-k) are of paramount interest for applications as gate layers in current and future integrated circuits. Here we report a lattice dynamics study of high-k Eu 2 O 3 films with thicknesses of 21.3, 2.2, 1.3, and 0.8 nm deposited on YSZ(001). The Eu-partial phonon density of states (PDOS), obtained from nuclear inelastic scattering, exhibits broadening of the phonon peaks accompanied by up to a four-fold enhancement of the number of low-energy states compared to the ab initio calculated PDOS of a perfect Eu 2 O 3 crystal. Our analysis demonstrates that while the former effect reflects the reduced phonon lifetimes observed in thin films due to scattering from lattice defects, the latter phenomenon arises from an ultrathin EuO layer formed between the thin Eu 2 O 3 film and the YSZ(001) substrate. Thus, our work uncovers another potential source of vibrational anomalies in thin films and multilayers, which has to be cautiously considered.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigation into the crystal structure–dielectric property correlation in barium titanate nanocrystals of different sizes

For high capacitance multilayer ceramic capacitors, high dielectric constant and lead-free ceramic nanoparticles are highly desired. However, as the particle size decreases to a few tens of nanometers, their dielectric constant significantly decreases, and the underlying mechanism has yet to be fully elucidated. Herein, we report a systematic investigation into the crystal structure–dielectric property relationship of combustion-made BaTiO 3 (BTO) nanocrystals. When the nanocrystal size was 100 nm and below, a metastable paraelectric cubic phase was found in the as-received BTO (denoted as arBTO) nanocrystals based on an X-ray diffraction (XRD) study. A stable ferroelectric tetragonal phase was present when the nanocrystal size was above 200 nm. Notably, the cubic arBTO (particle size ≤100 nm) exhibited tetragonal fluctuations as revealed by Raman spectroscopy, whereas the tetragonal arBTO (particle size ≥200 nm) contained ~10% cubic fraction according to the Rietveld fitting of the XRD profiles. Thermal annealing of the multi-grain tetragonal arBTO at 950 °C yielded single crystals of annealed BTO (denoted as anBTO), whose dielectric constants were higher than those of arBTO. However, the single crystalline anBTO prevented the formation of 90° domains; therefore, they exhibited a low dielectric constant of ~300. Although X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy could not identify the exact structural defects, our study revealed that surface and bulk defects formed during synthesis affect the final crystal structures and thus the dielectric properties of BTO nanocrystals with different sizes. Finally, the understanding obtained from this study will help us design high dielectric constant perovskite nanocrystals for next-generation multilayer ceramic capacitor applications.

36 MATERIALS SCIENCE↗

Technique for measurement of magnetostriction in an individual nanowire using atomic force microscopy

We have investigated a method for measuring the dimensions of an individual multilayered Fe-Ga/Cu nanowire (NW) as it changes with induced magnetization. In this study, we demonstrate the proposed approach and establish this as a viable method for measuring the magnetostrictive behavior of an individual Fe-Ga/Cu NW using atomic force microscopy (AFM). When an external magnetic field (∼300 Oe) was applied perpendicular to the NW axis, the NW length appeared minimized. When a field (∼1000 Oe) was applied parallel to the NW axis, the height profile of the NW was found to be higher than in the case with no parallel external field. Since both ends of the NW were welded to the substrate, the magnetic field induced dimensional change of the NW caused deflection of the NW in the upward direction, which was significant enough to be detected by AFM. An average height difference of 15 nm was measured with and without an applied field which was then used to calculate the magnetostriction of the multilayered NW.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Film growth, adsorption and desorption kinetics of indigo on SiO{sub 2}

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation of dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer desorption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanotechnology finding its way into flame retardancy

Nanotechnology is one of the key technologies of the 21{sup st} century. The exploitation of 'new' effects that arise from materials structured on the nano-scale has also been proposed successfully for flame retardancy of polymers since the end of the 90s. Of all of the approaches these include, at this time the use of nanocomposites offers the best potential for industrial application, also some other ideas are sketched, such as using electrospun nanofibers mats or layer-by-layer deposits as protection coatings, as well as sub-micrometer multilayer coatings as effective IR-mirrors. The general phenomena, inducing a flow limit in the pyrolysing melt and changing the fire residue, are identified in nanocomposites. Key experiments are performed such as quasi online investigation of the protection layer formation to understand what is going on in detail. The flame retardancy mechanisms are discussed and their impact on fire behaviour quantified. With the latter, the presentation pushes forward the state of the art. For instance, the heat shielding is experimentally quantified for a layered silicate epoxy resin nanocomposite proving that it is the only import mechanism controlling the reduction in peak heat release rate in the investigated system for different irradiations. The flame retardancy performance is assessed comprehensively illuminating not only the strengths but also the weak points of the concepts. Guidelines for materials development are deduced and discussed. Apart from inorganic fillers (layered silicate, boehmite, etc.) not only carbon nanoobjects such as multiwall carbon nanotubes, multilayer graphene and graphene are investigated, but also nanoparticles that are more reactive and harbor the potential for more beneficial interactions with the polymer matrix.

36 MATERIALS SCIENCE↗

Deformation sensor based on polymer-supported discontinuous graphene multi-layer coatings

Graphene can be conveniently used in the modification of polymer surfaces. Graphene macromolecules are perfectly transparent to the visible light and electrically conductive, consequently these two properties can be simultaneously provided to polymeric substrates by surface coating with thin graphene layers. In addition, such coating process provides the substrates of: water-repellence, higher surface hardness, low-friction, self-lubrication, gas-barrier properties, and many other functionalities. Polyolefins have a non-polar nature and therefore graphene strongly sticks on their surface. Nano-crystalline graphite can be used as graphene precursor in some chemical processes (e.g., graphite oxide synthesis by the Hummer method), in addition it can be directly applied to the surface of a polyolefin substrate (e.g., polyethylene) to cover it by a thin graphene multilayer. In particular, the nano-crystalline graphite perfectly exfoliate under the application of a combination of shear and friction forces and the produced graphene single-layers perfectly spread and adhere on the polyethylene substrate surface. Such polymeric materials can be used as ITO (indium-tin oxide) substitute and in the fabrication of different electronic devices. Here the fabrication of transparent resistive deformation sensors based on low-density polyethylene films coated by graphene multilayers is described. Such devices are very sensible and show a high reversible and reproducible behavior.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

On the transmission of terahertz radiation through silicon-based structures

We report on the transmission of a terahertz (THz) radiation through prototype structures based on a p-type silicon substrate. In particular, the bare substrate and progressively more complicated multilayer structures were investigated, allowing to address the effect on the transmission of different factors, such as the orientation of interdigitated contacts with respect to the polarized beam, the temperature, and the current flowing through a conductive SnO{sub 2} nanorods layer. A suitable experimental set-up was developed for the direct spectral measurement of transmission in the range of 0.75–1.1 THz at room and low temperatures. A simple Drude-Lorentz model was formulated, finding a quantitative agreement with the experimental transmission spectrum of the bare substrate at room temperature. For the multilayer structures, the spectra variations observed with temperature are well accounted by the corresponding change of the mobility of holes in the silicon p-type substrate. The influence of the contact orientation is consistent with that of a polarizing metallic grating. Finally, Joule heating effects are observed in the spectra performed as a function of the current flowing through the SnO{sub 2} nanorods layer. The experimental results shown here, together with their theoretical interpretation, provide insights for the development of devices fabricated on conductive substrates aimed to absorb/modulate radiation in the THz range.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Turning things downside up: Adsorbate induced water flipping on Pt(111)

We have examined the adsorption of the weakly bound species N{sub 2}, O{sub 2}, CO, and Kr on the (√(37)×√(37))R25.3{sup ∘} water monolayer on Pt(111) using a combination of molecular beam dosing, infrared reflection absorption spectroscopy, and temperature programmed desorption. In contrast to multilayer crystalline ice, the adsorbate-free water monolayer is characterized by a lack of dangling OH bonds protruding into the vacuum (H-up). Instead, the non-hydrogen-bonded OH groups are oriented downward (H-down) to maximize their interaction with the underlying Pt(111) substrate. Adsorption of Kr and O{sub 2} have little effect on the structure and vibrational spectrum of the “√(37)” water monolayer while adsorption of both N{sub 2}, and CO are effective in “flipping” H-down water molecules into an H-up configuration. This “flipping” occurs readily upon adsorption at temperatures as low as 20 K and the water monolayer transforms back to the H-down, “√(37)” structure upon adsorbate desorption above 35 K, indicating small energy differences and barriers between the H-down and H-up configurations. The results suggest that converting water in the first layer from H-down to H-up is mediated by the electrostatic interactions between the water and the adsorbates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Realizing in-plane surface diffraction by x-ray multiple-beam diffraction with large incidence angle

Based on rigorous dynamical-theory calculations, we demonstrate in this paper the principle of an x-ray multiple-beam diffraction (MBD) scheme that overcomes the long-lasting difficulties of high-resolution in-plane diffraction from crystal surfaces. This scheme only utilizes symmetric reflection geometry with large incident angles but activates the out-of-plane and in-plane diffraction processes simultaneously and separately in the continuous MBD planes. The in-plane diffraction is realized by detoured MBD, where the intermediate diffracted waves propagate parallel to the surface, which corresponds to an absolute Bragg surface diffraction configuration that is extremely sensitive to surface structures. Finally, a series of MBD diffraction and imaging techniques may be developed from this principle to study surface/interface (misfit) strains, lateral nanostructures, and phase transitions of a wide range of (pseudo)cubic crystal structures, including ultrathin epitaxial films and multilayers, quantum dots, strain-engineered semiconductor or (multi)ferroic materials, etc.

36 MATERIALS SCIENCE↗

Spin-orbit enhanced demagnetization rate in Co/Pt-multilayers

In order to explore the role of enhanced spin-orbit interactions on the laser-induced ultrafast magnetization dynamics, we performed a comparative study on cobalt thin films and Co/Pt multilayers. We show that the presence of the Co/Pt interfaces gives rise to a three-fold faster demagnetization upon femtosecond laser heating. Experimental data for a wide range of laser fluences are analyzed using the Microscopic 3-Temperature Model. We find that the Elliott-Yafet spin-flip scattering in the multilayer structure is increased by at least a factor of four with respect to the elementary Co film.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗