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At least 235 records · Page 13

Unusual Magnetic Hysteresis and Transition between Vortex and Double Pole States Arising from Interlayer Coupling in Diamond-Shaped Nanostructures

Controlling the magnetic ground states at the nanoscale is a long-standing basic research problem and an important issue in magnetic storage technologies. Here, we designed a nanostructured material that exhibits very unusual hysteresis loops due to a transition between vortex and double pole states. Arrays of 700 nm diamond-shaped nanodots consisting of Py(30 nm)/Ru(t Ru )/Py(30 nm) (Py, permalloy (Ni 80 Fe 20 )) trilayers were fabricated by interference lithography and e-beam evaporation. We show that varying the Ru interlayer spacer thickness (t Ru ) governs the interaction between the Py layers. We found this interaction mainly mediated by two mechanisms: magnetostatic interaction that favors antiparallel (antiferromagnetic, AFM) alignment of the Py layers and exchange interaction that oscillates between ferromagnetic (FM) and AFM couplings. For a certain range of Ru thicknesses, FM coupling dominates and forms magnetic vortices in the upper and lower Py layers. For Ru thicknesses at which AFM coupling dominates, the magnetic state in remanence is a double pole structure. Our results showed that the interlayer exchange coupling interaction remains finite even at 4 nm Ru thickness. Furthermore, the magnetic states in remanence, observed by magnetic force microscopy (MFM), are in good agreement with corresponding hysteresis loops obtained by the magneto-optic Kerr effect (MOKE) and micromagnetic simulations.

interlayer exchange interaction↗

Electronic Melting of Silicon in Nanostructures using X-ray Forbidden Bragg Reflections

Abstract We carried out a short beamtime at the Pohang Accelerator Laboratory x-ray Free Electron Laser to perform a pump-probe (PP) laser excitation diffraction experiment on the silicon (222) forbidden Bragg peak. To limit the x-ray penetration, we used a “device layer” silicon film wafer bonded to a silicon substrate. The sample, specially fabricated by MEMC Electronic Materials, had a Si(100) substrate bonded to a 170 nm Si(100) film rotated at 45° for crystallographic isolation. A second sample was reactive-ion-etched down to 52 nm thickness. In the silicon lattice, the covalent bonds are seen exclusively at the 222 reflection. Upon laser excitation, these electrons are expected to be excited to the valence band on femtosecond electronic time scales. The Si(222) reflection is therefore expected to be extinguished on this fast time scale, while the electron–phonon coupled acoustic response is determined by the lattice dynamics. The latter is determined by the speed of sound over the device thickness, which is in the mid-picosecond range.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Focused Helium Ion Beam for Direct Patterning of Monolayer MoS 2 Nanoribbon Field Effect Devices

The helium ion microscope (HIM) focused ion beam (FIB) has emerged as a powerful tool to directly pattern nanostructures below 10 nm due to its high-resolution capabilities and the inert nature of the ion source. These attributes make HIM FIB particularly interesting for patterning 2D materials such as transition metal dichalcogenides (TMDs) to investigate transport phenomena at the nanoscale. Reported here is the fabrication of MoS 2 nanoribbon devices using HIM FIB-induced etching (FIBIE) with XeF 2 , allowing for reduced ion dose compared to direct sputtering. While patterning is efficacious, the devices exhibit performance degradation with decreasing nanoribbon width due to damage up to 150 nm beyond the patterned edge. Incorporating an hBN encapsulation improves device performance by one order of magnitude, although the lateral extent of damage remains unchanged. The spatial distribution of damage is shown to be determined by the forward- and backscattered ions and electrons, while the hBN encapsulation layer substantially reduces damage from XeF 2 interactions in unexposed regions. Raman and photoluminescence (PL) measurements corroborate these findings, while ion/solid interaction simulations further elucidate the resolution limits imposed by substrate interactions. In conclusion, this work provides critical insights and a practical pathway for utilizing HIM FIBIE in 2D TMD functional device patterning.

MoS 2↗

Quantum simulation of an exotic quantum critical point in a two-site charge Kondo circuit

Tuning a material to the cusp between two distinct ground states can produce physical properties that are unlike those in either of the neighbouring phases. Advances in the fabrication and control of quantum systems have raised the tantalizing prospect of artificial quantum simulators that can capture such behaviour. A tunable array of coupled qubits should have an appropriately rich phase diagram, but realizing such a system with either tunnel-coupled semiconductor quantum dots or metal nanostructures has proven difficult. The challenge for scaling up to clusters or lattices is to ensure that each element behaves essentially identically and that the coupling between elements is uniform, while also maintaining tunability of the interactions. Here we study a nanoelectronic circuit comprising two coupled hybrid metal–semiconductor islands, combining the strengths of both materials to form a potentially scalable platform. The semiconductor component allows for controllable inter-site couplings at quantum point contacts, while the metal component’s effective continuum of states means that different sites can be made equivalent by tuning local potentials. The couplings afforded by this architecture can realize an unusual quantum critical point resulting from frustrated Kondo interactions. In this study, the observed critical behaviour matches theoretical predictions, verifying the success of our experimental quantum simulation.

36 MATERIALS SCIENCE↗

TiO 2 Nanocoatings with Controllable Crystal Type and Nanoscale Topography on Zirconia Implants to Accelerate Bone Formation

In dentistry, zirconia implants have emerged as a promising alternative for replacing missing teeth due to their superior aesthetic performance and chemical stability. To improve the osseointegration of zirconia implants, modifying their surface with hierarchical micro/nanotopography and bioactive chemical composition are two effective ways. In this work, a microscale topography was prepared on a zirconia surface using hydrofluoric acid etching, and then a 50 nm TiO 2 nanocoating was deposited via atomic layer deposition (ALD). Subsequently, an annealing treatment was used to transform the TiO 2 from amorphous to anatase and simultaneously generate nanoscale topography. Various investigations into the coating surface morphology, topography, wettability, and chemical composition were carried out using scanning electron microscopy, white light interferometry, contact‐angle measurement, X‐ray diffraction, and X‐ray photoelectron spectroscopy. In addition, in vitro cytocompatibility and osteogenic potential performance of the coatings were evaluated by human bone marrow mesenchymal stem cells (hBMSCs), and in vivo osseointegration performance was assessed in a rat femoral condyle model. Moreover, the possible mechanism was also investigated. The deposition of TiO 2 film with/without annealing treatment did not alter the microscale roughness of the zirconia surface, whereas the nanotopography changed significantly after annealing. The in vitro studies revealed that the anatase TiO 2 coating with regular wavelike nanostructure could promote the adhesion and proliferation of osteoblasts and further improve the osteogenic potential in vitro and osseointegration in vivo. These positive effects may be caused by nanoscale topography via the canonical Wnt/ β ‐catenin pathway. The results suggest that using ALD in combination with annealing treatment to fabricate a nanotopographic TiO 2 coating is a promising way to improve the osteogenic properties of zirconia implants.

Li, Nan (ORCID:0000000255156737)↗

Access to Advanced Functional Materials through Postmodification of Biomimetic Assemblies via Click Chemistry

The design, synthesis, and fabrication of functional nanomaterials with specific properties remain a long-standing goal for many scientific fields. The self-assembly of sequence-defined biomimetic synthetic polymers presents a fundamental strategy to explore the chemical space beyond biological systems to create advanced nanomaterials. Moreover, subsequent chemical modification of existing nanostructures is a unique approach for accessing increasingly complex nanostructures and introducing functionalities. Of these modifications, covalent conjugation chemistries, such as the click reactions, have been the cornerstone for chemists and materials scientists. Herein, we highlight some recent advances that have successfully employed click chemistries for the postmodification of assembled one-dimensional (1D) and two-dimensional (2D) nanostructures to achieve applications in molecular recognition, mineralization, and optoelectronics. Specifically, biomimetic nanomaterials assembled from sequence-defined macromolecules such as peptides and peptoids are described.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Toward Thermally Stimuli-Responsive Polymeric Vesicles Fabricated by Block Copolymer Blends for Nanocarriers

Polymeric vesicles, characterized by enhanced colloidal stability, excellent mechanical properties, controllable surface functionality, and adjustable membrane thickness, are extremely useful in nano- and bio-technology for potential applications as nanosized carriers for drugs and enzymes. However, a few preparative steps are necessary to achieve a unilamellar vesicle with a narrow size distribution. Herein, we report the spontaneous formation of unilamellar polymeric vesicles with nanometer sizes (<50 nm), fabricated by simply mixing diblock copolymers (P(EO-AGE)(2K-2K) and P(EO-AGE)(0.75K-2K)) with differing hydrophilic mass fractions in aqueous solutions. Depending on the mixing ratio of block copolymers and the temperature, the block copolymer mixtures self-assemble into various nanostructures, such as spherical and cylindrical micelles, or vesicles. The self-assembled structures of the block copolymer mixtures were characterized by small-angle neutron scattering, resulting in a phase diagram drawn as a function of temperature and the mixing condition. Notably, the critical temperature for the micelle-to-vesicle phase transition can be easily controlled by altering the mixing conditions; it decreases with an increase in the concentration of one of the block copolymers.

block copolymers↗

Fabrication of Advanced Nanocarbon-Metal Composites for Improved Energy Efficiency

We fabricated nanocarbon metal composites (NCMC) of Al alloys with a process called “electrocharging assisted process” (EAP). This method consists of the application of a high current to a mixture of liquid metal and carbon particles. We investigated aluminum alloys (6061 and 1350) and used activated carbon and graphite powder as the source of carbon. The high current induces the formation of carbon chains and ribbons in the liquid metal. Upon solidification of the metal an epitaxial relation between the carbon nanostructures and the metal lattice is produced. The purpose of the project was to find the parameters during the reaction that would give rise to a high density of nanoribbons extending throughout the metal such that the electrical conductivity and the mechanical strength of the composite increased and that the method could be extended to large scale manufacturing. For this purpose, we designed two reactors for the incorporation of nanocarbon ribbons in aluminum metal. The first reactor was designed to have more control of the region with the high current density. However, there were problems with getting good mixing of the carbon in small volumes. A second reactor was designed with a stirrer that allowed for better mixing of the carbon by the introduction of argon gas through the shaft of the stirrer. NCMC were fabricated with a series of parameters to understand the role of current, time of applied current, type and shape of the cathode electrode and stirring speed of the mixture. We analyzed the composites by Raman scattering to gain information on the crystallite size of the nanocarbon, XRD to obtain the crystal structure of the composite, SEM and TEM to characterize the grain size of the aluminum grains and the quality of the crystal structure. We also measured the electrical conductivity and mechanical properties of selected samples. The nanocomposites showed increase in crystallite size of the nanocarbon with a linear dependence of the crystallite size on the duration of the applied current. There is a minimum current density necessary for the crystallite size to increase compared to the ~ 10 nm size of the activated carbon source used in the fabrication. The electrical conductivity of the nanocomposites increased with crystallite size of the nanocarbon and with the concentration of converted carbon. The maximum increase in electrical conductivity was 5.7% above the baseline for samples with ~ 4 wt % nanocarbon with crystallite size larger than 30 nm. These samples presented a hardness ~ 8% higher than the baseline samples with no carbon.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Role of nanoparticle size and surface chemistry on ion transport and nanostructure of perfluorosulfonic acid ionomer nanocomposites

In this work, we present a systematic investigation of the impact of silica nanoparticle (SiNP) size and surface chemistry on the nanoparticle dispersion state and the resulting morphology and vanadium ion permeability of the composite ionomer membranes. Specifically, Nafion containing a mass fraction of 5% silica particles, ranging in nominal diameters from 10 nm to >1 μm and with both sulfonic acid- and amine-functionalized surfaces, was fabricated. Most notably, an 80% reduction in vanadium ion permeability was observed for ionomer membranes containing amine-functionalized SiNPs at a nominal diameter of 200 nm. Further, these membranes exhibited an almost 400% increase in proton selectivity when compared to pristine Nafion. Trends in vanadium ion permeability within a particular nominal diameter were seen to be a function of the surface chemistry, where, for example, vanadyl ion permeability was observed to increase with increasing particle size for membranes containing unfunctionalized SiNPs, while it was seen to remain relatively constant for membranes containing amine-functionalized SiNPs. In general, the silica particles tended to exhibit a higher extent of aggregation as the size of the particles was increased. From small-angle neutron scattering experiments, an increase in the spacing of the hydrophobic domains was observed for all composite membranes, though particle size and surface chemistry were seen to have varying impacts on the spacing of the ionic domains of the ionomer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Emulsion stereolithography and 3D printing of multimaterials and nanoscale material gradients

A functionally graded material is formed by pipetting individual micro-or-nano-litter droplets with a variety of materials including multi-nanostructured material (nanowires, carbon nanotubes, enzymes, multi-element and/or multi-color, multi-biomolecules) and UV polymerization of the flat hydrogel meniscus surface formed at the carrier fluid interface. After step-by-step droplet pipetting and subsequent layer-by-layer UV polymerization via a digital mask, the complete fabricated part without supporting layers is taken out of the carrier fluid while the un-cured micro-litter residue is conveniently suctioned out of the carrier fluid.

Zheng, Xiaoyu↗

Electronically reconfigurable complex oxide heterostructure freestanding membranes

In recent years, lanthanum aluminate/strontium titanate (LAO/STO) heterointerfaces have been used to create a growing family of nanoelectronic devices based on nanoscale control of LAO/STO metal-to-insulator transition. The properties of these devices are wide-ranging, but they are restricted by nature of the underlying thick STO substrate. Here, single-crystal freestanding membranes based on LAO/STO heterostructures were fabricated, which can be directly integrated with other materials via van der Waals stacking. The key properties of LAO/STO are preserved when LAO/STO membranes are formed. Conductive atomic force microscope lithography is shown to successfully create reversible patterns of nanoscale conducting regions, which survive to millikelvin temperatures. The ability to form reconfigurable conducting nanostructures on LAO/STO membranes opens opportunities to integrate a variety of nanoelectronics with silicon-based architectures and flexible, magnetic, or superconducting materials.

36 MATERIALS SCIENCE↗

Functional composites by programming entropy-driven nanosheet growth

Here, nanomaterials must be systematically designed to be technologically viable. Driven by optimizing intermolecular interactions, current designs are too rigid to plug in new chemical functionalities and cannot mitigate condition differences during integration. Despite extensive optimization of building blocks and treatments, accessing nanostructures with the required feature sizes and chemistries is difficult. Programming their growth across the nano-to-macro hierarchy also remains challenging, if not impossible. To address these limitations, we should shift to entropy-driven assemblies to gain design flexibility, as seen in high-entropy alloys, and program nanomaterial growth to kinetically match target feature sizes to the mobility of the system during processing. In tis report, following a micro-then-nano growth sequence in ternary composite blends composed of block-copolymer-based supramolecules, small molecules and nanoparticles, we successfully fabricate high-performance barrier materials composed of more than 200 stacked nanosheets (125 nm sheet thickness) with a defect density less than 0.056 µm -2 and about 98% efficiency in controlling the defect type. Contrary to common perception, polymer-chain entanglements are advantageous to realize long-range order, accelerate the fabrication process (<30 min) and satisfy specific requirements to advance multilayered film technology. This study showcases the feasibility, necessity and unlimited opportunities to transform laboratory nanoscience into nanotechnology through systems engineering of self-assembly.

42 ENGINEERING↗

High-performance cementitious composites containing nanostructured carbon additives made from charred coal fines

Carbon-based nanomaterials, such as carbon nanoplatelets, graphene oxide, and carbon quantum dots, have many possible end-use applications due to their ability to impart unique mechanical, electrical, thermal, and optical properties to cement composites. Despite this potential, these materials are rarely used in the construction industry due to high material costs and limited data on performance and durability. In this study, domestic coal is used to fabricate low-cost carbon nanomaterials that can be used economically in cement formulations. A range of chemical and physical processing approaches are employed to control the size, morphology, and chemical functionalization of the carbon nanomaterial, which improves its miscibility with cement formulations and its impact on mechanical properties and durability. At loadings of 0.01 to 0.07 wt.% of coal-derived carbon nanomaterial, the compressive and flexural strength of cement samples are enhanced by 24% and 23%, respectively, in comparison to neat cement. At loadings of 0.02 to 0.06 wt.%, the compressive and flexural strength of concrete composites increases by 28% and 21%, respectively, in comparison to neat samples. Additionally, the carbon nanomaterial additives studied in this work reduce cement porosity by 36%, permeability by 86%, and chloride penetration depth by 60%. These results illustrate that low-loadings of coal-derived carbon nanomaterial additives can improve the mechanical properties, durability, and corrosion resistance of cement composites.

36 MATERIALS SCIENCE↗

Single Wall Carbon Nanotube-polymer Solar Cells

Investigation of single wall carbon nanotube (SWNT)-polymer solar cells has been conducted towards developing alternative lightweight, flexible devices for space power applications. Photovoltaic devices were constructed with regioregular poly(3-octylthiophene)-(P3OT) and purified, >95% w/w, laser-generated SWNTs. The P3OT composites were deposited on ITO-coated polyethylene terapthalate (PET) and I-V characterization was performed under simulated AM0 illumination. Fabricated devices for the 1.0% w/w SWNT-P3OT composites showed a photoresponse with an open-circuit voltage (V(sub oc)) of 0.98 V and a short-circuit current density (I(sub sc)) of 0.12 mA/sq cm. Optimization of carrier transport within these novel photovoltaic systems is proposed, specifically development of nanostructure-SWNT complexes to enhance exciton dissociation.

Bailey, Sheila G.↗

Emergent Collective Phenomena in Artificial Spin Ice (Final Technical Report)

This program encompassed studies of lithographically fabricated “artificial spin ice” arrays of nanometer-scale single-domain ferromagnetic islands in which the array geometry results in frustration of the magnetostatic interactions between the islands. Artificial spin ice offers a wide range of opportunities for studying the mechanism by which nature accommodates frustration and accesses physics associated with frustration in ferromagnetic nanostructures. Since the arrays are created lithographically, we can easily vary the array characteristics, including the geometry of the lattice and the level and type of lattice disorder. We can probe both the local properties of the arrays by imaging individual moments, and we can also probe thousands of moments simultaneously, allowing us to gain insight into the collective properties of the system. The research funded by this program included studies of unusual frustrated lattices, studies of magnetotransport in these systems, studies of perpendicular anisotropy moments, and a range of other related experimental measurements.

36 MATERIALS SCIENCE↗

Shape evolution and growth mechanisms of 3D-printed nanowires

3D printing of nanowires using Focused Electron Beam Induced Deposition (FEBID) enables the direct-write fabrication of complex 3D objects on almost any substrate surface. The physical properties of such freestanding structures are determined by the dimensions of constituent nanowires. However, little knowledge is available about the exact shape of the nanowires, which is indispensable for calculations and simulations as well as for optimization in applications. In this study, we evaluate the thicknesses and widths of freestanding segments as a function of the inclination angles, primary electron energy, beam currents, and precursor flux. Furthermore, the cross-sectional shape, the cross-sectional area, and the evolution along the length of the wire are investigated. Basing on detailed scanning electron microscopy measurements and Monte Carlo/Finite Differences simulations, the effects that the growth parameters have on the segment growth are elucidated. Furthermore, the results shed light on the growth evolution of the structures and form the basis for future studies on the fabrication of high-precision, arbitrarily shaped nanowires.

36 MATERIALS SCIENCE↗

Engineering of Self‐Aggregation‐Resistant MnO 2 Heterostructure with A Built‐in Field for Enhanced High‐Mass‐Loading Energy Storage

Abstract Although MnO 2 has been intensively investigated for energy storage, further applications are limited by van der Waals force‐triggered self‐aggregation that always leads to poorly exposed active sites and compromised reaction dynamics, especially under high‐mass‐loading conditions. Herein, by synergistically coupling interfacial modulation with the Kirkendall effect, this work achieves in situ topological structure reorganization of MnOOH toward the high‐aspect‐ratio MnO 2 heterostructure (Heter‐MnO 2 ) with fully exposed active sites, which is ready to assemble into self‐supporting high‐mass‐loading film (30 mg cm −2 ) with restrained self‐aggregation. Theoretical calculation and dynamics analysis results demonstrate the generation of the built‐in field within the heterostructure, thus enhancing the electronic‐transfer and ionic‐adsorption/transport rates. As such, the 30 mg cm −2 Heter‐MnO 2 electrode achieves a superior areal capacitance of 4762 mF cm −2 at 1 mA cm −2 and a sound rate performance (79% at 100 mA cm −2 ) comparable to those of low‐mass‐loading/thin‐film electrodes. As a proof of concept, the fabricated planar interdigital quasi‐solid‐state symmetric micro‐supercapacitor (MSC) based on the Heter‐MnO 2 electrode can deliver a remarkable areal capacitance of 181 mF cm −2 and a considerable volumetric energy density of 10.3 mWh cm −3 . This methodology highlights the promise of surface/interface chemistry modulation for the configuration of easy‐to‐integrate hierarchical nanostructures to better meet practical energy applications.

Chemistry↗

MoS 2 -Decorated Graphene@porous Carbon Nanofiber Anodes via Centrifugal Spinning

Sodium-ion batteries (SIBs) are promising alternatives to lithium-ion batteries as green energy storage devices because of their similar working principles and the abundance of low-cost sodium resources. Nanostructured carbon materials are attracting great interest as high-performance anodes for SIBs. Herein, a simple and fast technique to prepare carbon nanofibers (CNFs) is presented, and the effects of carbonization conditions on the morphology and electrochemical properties of CNF anodes in Li- and Na-ion batteries are investigated. Porous CNFs containing graphene were fabricated via centrifugal spinning, and MoS 2 were decorated on graphene-included porous CNFs via hydrothermal synthesis. The effect of MoS 2 on the morphology and the electrode performance was examined in detail. The results showed that the combination of centrifugal spinning, hydrothermal synthesis, and heat treatment is an efficient way to fabricate high-performance electrodes for rechargeable batteries. Furthermore, CNFs fabricated at a carbonization temperature of 800 °C delivered the highest capacity, and the addition of MoS 2 improved the reversible capacity up to 860 mAh/g and 455 mAh/g for Li- and Na-ion batteries, respectively. A specific capacity of over 380 mAh/g was observed even at a high current density of 1 A/g. Centrifugal spinning and hydrothermal synthesis allowed for the fabrication of high-performance electrodes for sodium ion batteries.

25 ENERGY STORAGE↗