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Table of contents

Volume 28

Number 9, 3 March 2017

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Topical Review

092001

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Remarkable progress has been made in the field of one-dimensional semiconductor nanostructures for electronic and photonic devices. Group-IV semiconductors and their heterostructures have dominated the years of success in microelectronic industry. However their use in photonic devices is limited since they exhibit poor optical activity due to indirect band gap nature of Si and Ge. Reducing their dimensions below a characteristic length scale of various fundamental parameters like exciton Bohr radius, phonon mean free path, critical size of magnetic domains, exciton diffusion length etc result in the significant modification of bulk properties. In particular, light emission from Si/Ge nanowires due to quantum confinement, strain induced band structure modification and impurity doping may lead to the integration of photonic components with mature silicon CMOS technology in near future. Several promising applications based on Si and Ge nanowires have already been well established and studied, while others are now at the early demonstration stage. The control over various forms of energy and carrier transport through the unconstrained dimension makes Si and Ge nanowires a promising platform to manufacture advanced solid-state devices. This review presents the progress of the research with emphasis on their potential application of Si/Ge nanowires and their heterostructures for electronic, photonic, sensing and energy devices.

Focus Issue Paper

094001

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Focus on graphene and related materials

The focus of this study is to design new nano-modified epoxy formulations using carbon nanofillers, such as carbon nanotubes, carbon nanofibers and graphene-based nanoparticles (CpEG), that reduce the moisture content and provide additional functional performance. The chemical structure of epoxy mixture, using a non-stoichiometric amount of hardener, exhibits unique properties in regard to the water sorption for which the equilibrium concentration of water (Ceq) is reduced up to a maximum of 30%. This result, which is very relevant for several industrial applications (aeronautical, shipbuilding industries, wind turbine blades, etc), is due to a strong reduction of the polar groups and/or sites responsible to bond water molecules. All nanofillers are responsible of a second phase at lower glass transition temperature (Tg). Compared with other carbon nanofillers, functionalized graphene-based nanoparticles exhibit the best performance in the multifunctionality. The lowest moisture content, the high performance in the mechanical properties, the low electrical percolation threshold (EPT) have been all ascribed to particular arrangements of the functionalized graphene sheets embedded in the polymeric matrix. Exfoliation degree and edge carboxylated groups are responsible of self-assembled architectures which entrap part of the resin fraction hindering the interaction of water molecules with the polar sites of the resin, also favouring the EPT paths and the attractive/covalent interactions with the matrix.

Papers

Biology and medicine

095101

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Premature cellular senescence refers to the state of irreversible cell cycle arrest due to DNA damage or other stresses. In this study, CD9 monoclonal antibody (CD9mAb) was successfully conjugated to the surface of PEGylated liposomes for targeted delivery of rapamycin (LR-CD9mAb) to overcome senescence of CD9 receptor-overexpressing cells. LR-CD9mAb has a small particle size (143.3 ± 2.4 nm), narrow size distribution (polydispersity index: 0.220 ± 0.036), and negative zeta potential (−14.6 ± 1.2 mV). The uptake of CD9-targeted liposomes by premature senescent human dermal fibroblasts (HDFs) was higher than that by young HDFs, as displayed by confocal microscopic images. The senescence might not be reversed by treatment with rapamycin; however, the drug promoted cell proliferation and reduced the number of cells that expressed the senescence-associated-β-galactosidase (SA-β-gal). These effects were further confirmed by cell viability, cell cycle, and Western blotting analyses. Moreover, CD9-targeted liposomes showed better anti-senescence activity, in comparison with free rapamycin or the conventional liposomal formulation, suggesting the potential application of this system in further in vivo studies.

095102

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Drug-resistant bacteria are an increasingly serious threat to global public health. In particular, infections from multidrug-resistant (MDR) Gram-positive bacteria (i.e. Staphylococcus aureus) are growing global health concerns. In this work, we report the first use of nanoscale metal-organic frameworks (NMOFs) coencapsulating an antibiotic (vancomycin) and targeting ligand (folic acid) in one pot to enhance therapeutic efficacy against MDR S. aureus. Zeolitic imidazolate framework (ZIF-8) NMOFs, which have globular morphologies coencapsulating vancomycin and folic acid, are characterized by transmission electron microscopy, field-emission scanning electron microscopy, powder x-ray diffraction, ulltraviolet–visible spectroscopy, and dynamic light-scattering techniques. We determined that the presence of folic acid on the surface of the NMOFs is significant in the sense of effective uptake by MDR S. aureus through endocytosis. The functionalized NMOFs transport vancomycin across the cell wall of MDR S. aureus and enhance antibacterial activity, which has been confirmed from studies of the minimum inhibitory concentration, minimum bactericidal concentration, cytotoxicity of bacterial cells, and generation of reactive oxygen species. This work shows that functionalized NMOFs hold great promise for effective treatment of MDR S. aureus.

Electronics and photonics

095201

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We report a highly efficient tunable THz reflector in graphene. By applying a small gate voltage (up to ±3 V), the reflectance of graphene is modulated from a minimum of 0.79% to a maximum of 33.4% using graphene/ionic liquid structures at room temperature, and the reflection tuning is uniform within a wide spectral range (0.1–1.5 THz). Our observation is explained by the Drude model, which describes the THz wave-induced intraband transition in graphene. This tunable reflectance of graphene may contribute to broadband THz mirrors, deformable THz mirrors, variable THz beam splitters and other optical components.

095202

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We investigate a series of Ag–Al thin films containing up to 12 at% Al with the purpose of discovering whether these alloys would be a better choice for nanophotonic applications than pure Ag. Variable angle spectroscopic ellipsometry, AFM, x-ray diffraction and density functional theory are applied to explore and characterize the materials. Electromagnetic simulations of optical properties are used to place the results into a theoretical framework. We find that the increase in electron-to-atom ratio associated with the Al additions changes the optical properties: additions of the order of 1–2 at% Al are beneficial as they are associated with favorable changes in the dielectric function, but for greater additions of Al there is a flattening of the absorption edge and an increase in optical loss. In addition, contents of more than about 2 at% Al are associated with the onset of time-dependent intergranular oxidation, which causes a pronounced dip in the reflectance spectrum at about 2.3–2.4 eV (∼500–540 nm).

095203

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Organic bistable memory devices were fabricated by embedding a thin layer of molybdenum trioxide (MoO3) between two tris-(8-hydroxyquinoline)aluminum (Alq3) layers. The device exhibited excellent switching characteristics with an ON/OFF current ratio of 1.15 × 103 at a read voltage of 1 V. The device showed repeatable write–erase capability and good stability in both the conductance states. These conductance states are non-volatile in nature and can be obtained by applying appropriate voltage pulses. The effect of MoO3 layer thickness and its location in the Alq3 matrix on characteristics of the memory device was investigated. The field emission scanning electron microscopy (FE-SEM) images of the MoO3 layer revealed the presence of isolated nanoparticles. Based on the experimental results, a mechanism has been proposed for explaining the conductance switching of fabricated devices.

095204

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Fabrication of small-sized patterns of inorganic semiconductor onto flexible substrates is a major concern when manufacturing wearable devices for measuring either biometric or environmental parameters. In this study, micro-sized flexible ZnO UV photodetectors have been thoroughly prepared by a facile inkjet printing technology and followed with heat treatments. A simple ink recipe of zinc acetate precursor solution was investigated. It is found that the substrate temperature during zinc precursor ink depositing has significant effects on ZnO pattern shape, film morphology, and crystallization. The device fabricated from the additive manufacturing approach has good bendability, Ohmic contact, short response time as low as 0.3 s, and high on/off ratio of 3525. We observed the sensor's dependence of response/decay time by the illuminating UV light intensity. The whole process is based on additive manufacturing which has many benefits such as rapid prototyping, saving material, being environmentally friendly, and being capable of creating high-resolution patterns. In addition, this method can be applied to flexible substrates, which makes the device more applicable for applications requiring flexibility such as wearable devices. The proposed all-inkjet-printing approach for a micro-sized ZnO UV photodetector would significantly simplify the fabrication process of micro-sized inorganic semiconductor-based devices. A potential application is real-time monitoring of UV light exposure to warn users about unsafe direct sunlight to implement suitable avoidance solutions.

095205

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The results are presented for luminescent solar concentrators (LSCs) fabricated with poly(lauryl methacrylate-co-ethylene glycol dimethacrylate) (P(LMA-co-EGDMA)) and Angstrom Bond, Inc. AB9093 acrylic epoxy matrix, high quantum yield (> 70%) PbSe quantum dots (QDs) and silicon photovoltaic (Si PV) cells. LSCs were tested under a lamp with broadband illumination, photon flux-matched to a standard solar spectrum and verified under a calibrated solar lamp source. The P(LMA-co-EGDMA) sample demonstrated the highest power conversion efficiency of any known LSC fabricated with either QDs or Si PV cells, 4.74%. Additionally, increased temperature was shown to reduce efficiency.

095206

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Vertically aligned gallium nitride (GaN) nanowire (NW) arrays have attracted a lot of attention because of their potential for novel devices in the fields of optoelectronics and nanoelectronics. In this work, GaN NW arrays have been designed and fabricated by combining suitable nanomachining processes including dry and wet etching. After inductively coupled plasma dry reactive ion etching, the GaN NWs are subsequently treated in wet chemical etching using AZ400K developer (i.e., with an activation energy of 0.69 ± 0.02 eV and a Cr mask) to form hexagonal and smooth a-plane sidewalls. Etching experiments using potassium hydroxide (KOH) water solution reveal that the sidewall orientation preference depends on etchant concentration. A model concerning surface bonding configuration on crystallography facets has been proposed to understand the anisotropic wet etching mechanism. Finally, NW array-based vertical field-effect transistors with wrap-gated structure have been fabricated. A device composed of 99 NWs exhibits enhancement mode operation with a threshold voltage of 1.5 V, a superior electrostatic control, and a high current output of >10 mA, which prevail potential applications in next-generation power switches and high-temperature digital circuits.

095207

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We investigate the effects of water absorption on the electrical performance and stability in high-mobility zinc oxynitride (ZnON) thin-film transistors (TFTs). The ZnON TFT exhibits a smaller field-effect mobility, lower turn-on voltage, and higher subthreshold slope with a deteriorated electrical stability under positive gate bias stresses after being exposed to water. From the Hall measurements, an increase of the electron concentration and a decrease of the Hall mobility are observed in the ZnON thin film after water absorption. The observed phenomena are mainly attributed to the water molecule-induced increase of the defective ZnXNY bond and the oxygen vacancy inside the ZnON thin film based on the x-ray photoelectron spectroscopy analysis.

Patterning and nanofabrication

095301

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How to use high aspect ratio anodic aluminum oxide (AAO) membranes as an etching and evaporation mask is one of the unsolved problems in the application of nanostructured arrays. Here we describe the versatile utilizations of the highly ordered AAO membranes with a high aspect ratio of more than 20 used as universal masks for the formation of various nanostructure arrays on various substrates. The result shows that the fabricated nanopore and nanoparticle arrays of substrates inherit the regularity of the AAO membranes completely. The flat AAO substrates and uneven AAO frontages were attached to the Si substrates respectively as an etching mask, which demonstrates that the two kinds of replication, positive and negative, represent the replication of the mirroring of Si substrates relative to the flat AAO substrates and uneven AAO frontages. Our work is a breakthrough for the broad research field of surface nano-masking.

095302

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Microelectrode arrays (MEAs) are gaining increasing importance for the investigation of signaling processes between electrogenic cells. However, efficient cell–chip coupling for robust and long-term electrophysiological recording and stimulation still remains a challenge. A possible approach for the improvement of the cell–electrode contact is the utilization of three-dimensional structures. In recent years, various 3D electrode geometries have been developed, but we are still lacking a fabrication approach that enables the formation of different 3D structures on a single chip in a controlled manner. This, however, is needed to enable a direct and reliable comparison of the recording capabilities of the different structures. Here, we present a method for a precisely controlled deposition of nanoelectrodes, enabling the fabrication of multiple, well-defined types of structures on our 64 electrode MEAs towards a rapid-prototyping approach to 3D electrodes.

Energy at the nanoscale

095401

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Flexible piezoelectric nanogenerators (PNGs) based on a composite of ZnO nanorods (NRs) and an array of Si micro-pillars (MPs) are demonstrated by a transfer process. The flexible composite structure was fabricated by hydrothermal growth of ZnO NRs on an electrochemically etched Si MP array with various lengths followed by mechanically delaminating the Si MP arrays from the Si substrate after embedding them in a polydimethylsiloxane matrix. Because the Si MP arrays act as a supporter to connect the ZnO NRs electrically and mechanically, verified by capacitance measurement, the output voltage from the flexible PNGs increased systematically with the increased density ZnO NRs depending on the length of the Si MPs. The flexible PNGs showed 3.2 times higher output voltage with a small change in current with increasing Si MP length from 5 to 20 μm. The enhancement of the output voltage is due to the increased number of series-connected ZnO NRs and the beneficial effect of a ZnO NR/Si MP heterojunction on reducing free charge screening effects. The flexible PNGs can be attached on fingers as a wearable electrical power source or motion sensor.

095402

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Germanium exhibits high charge capacity and high lithium diffusivity, both are the key requirements for electrode materials in high performance lithium ion batteries (LIBs). However, high volume expansion and segregation from the electrode during charge–discharge cycling have limited use of germanium in LIBs. Here, we demonstrate that ZnO decorated Ge nanoparticles (Ge@ZnO NPs) can overcome these limitations of Ge as an LIB anode material. We produced Ge NPs at high rates by laser pyrolysis of GeH4, then coated them with solution phase synthesized ZnO NPs. Half-cell tests revealed dramatically enhanced cycling stability and higher rate capability of Ge@ZnO NPs compared to Ge NPs. Enhancements arise from the core–shell structure of Ge@ZnO NPs as well as production of metallic Zn from the ZnO layer. These findings not only demonstrate a new surface treatment for Ge NPs, but also provide a new opportunity for development of high-rate LIBs.

095403

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We study the conversion efficiency of an energy harvester based on resonant tunneling through quantum dots with heat leakage. Heat leakage current from a hot electrode to a cold electrode is taken into account in the analysis of the harvester operation. Modeling of electrical output indicates that a maximum heat leakage current is not negligible because it is larger than that of the heat current harvested into electrical power. A reduction of heat leakage is required in this energy harvester in order to obtain efficient heat-to-electrical conversion. Multiple energy levels of a quantum dot can increase the output power of the harvester. Heavily doped colloidal semiconductor quantum dots are a possible candidate for a quantum-dot monolayer in the energy harvester to reduce heat leakage, scaling down device size, and increasing electrical output via multiple discrete energy levels.

Sensing and actuating

095501

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This paper reports a new type of electronic, recoverable skin-like pressure and strain sensor, produced on a flexible, biodegradable pencil-eraser substrate and fabricated using a solvent-free, low-cost and energy efficient process. Multi-walled carbon nanotube (MWCNT) film, the strain sensing element, was patterned on pencil eraser with a rolling pin and a pre-compaction mechanical press. This induces high interfacial bonding between the MWCNTs and the eraser substrate, which enables the sensor to achieve recoverability under ambient conditions. The eraser serves as a substrate for strain sensing, as well as acting as a dielectric for capacitive pressure sensing, thereby eliminating the dielectric deposition step, which is crucial in capacitive-based pressure sensors. The strain sensing transduction mechanism is attributed to the tunneling effect, caused by the elastic behavior of the MWCNTs and the strong mechanical interlock between MWCNTs and the eraser substrate, which restricts slippage of MWCNTs on the eraser thereby minimizing hysteresis. The gauge factor of the strain sensor was calculated to be 2.4, which is comparable to and even better than most of the strain and pressure sensors fabricated with more complex designs and architectures. The sensitivity of the capacitive pressure sensor was found to be 0.135 MPa−1.To demonstrate the applicability of the sensor as artificial electronic skin, the sensor was assembled on various parts of the human body and corresponding movements and touch sensation were monitored. The entire fabrication process is scalable and can be integrated into large areas to map spatial pressure distributions. This low-cost, easily scalable MWCNT pin-rolled eraser-based pressure and strain sensor has huge potential in applications such as artificial e-skin in flexible electronics and medical diagnostics, in particular in surgery as it provides high spatial resolution without a complex nanostructure architecture.

095502

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Surface-area-controlled porous TiO2 thin films were prepared via a simple sol–gel chemical route, and their gas-sensing properties were thoroughly investigated in the presence of typical oxidizing NO2 gas. The surface area of TiO2 thin films was controlled by developing porous TiO2 networked by means of controlling the TiO2-to-TTIP (titanium isopropoxide, C12H28O4Ti) molar ratio, where TiO2 nanoparticles of size ∼20 nm were used. The sensor's response was found to depend on the surface area of the TiO2 thin films. The porous TiO2 thin-film sensor with greater surface area was more sensitive than those of TiO2 thin films with lesser surface area. The improved sensing ability was ascribed to the porous network formed within the thin films by TiO2 sol. Our results show that surface area is a key parameter for obtaining superior gas-sensing performance; this provides important guidelines for preparing and using porous thin films for gas-sensing applications.

Materials: properties, characterization or tools

095701

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We study the emission dynamics of semiconductor quantum dots in the presence of the correlated impact of metal oxides and dielectric materials. For this we used layered material structures consisting of a base substrate, a dielectric layer, and an ultrathin layer of a metal oxide. After depositing colloidal CdSe/ZnS quantum dots on the top of the metal oxide, we used spectral and time-resolved techniques to show that, depending on the type and thickness of the dielectric material, the metal oxide can characteristically change the interplay between intrinsic excitons, defect states, and the environment, offering new material properties. Our results show that aluminum oxide, in particular, can strongly change the impact of amorphous silicon on the emission dynamics of quantum dots by balancing the intrinsic near band emission and fast trapping of carriers. In such a system the silicon/aluminum oxide charge barrier can lead to large variation of the radiative lifetime of quantum dots and control of the photo-ejection rate of electrons in quantum dots. The results provide unique techniques to investigate and modify physical properties of dielectrics and manage optical and electrical properties of quantum dots.

095702
The following article is Open access

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Small-scale samples enable us to understand changes in physical properties under larger strain due to their higher tolerance to deformation. In this study, the piezoresistive character of n-type 〈111〉-oriented Si nanowires under large strain was measured during tensile and compressive deformations. The Si nanowires were directly cut from the wafer using top-down technology and deformed while capturing their electrical properties inside a transmission electron microscope. The experimental results show that both tensile and compressive deformation enhanced their electrical transport properties. The piezoresistance coefficient is of the same order of magnitude as its bulk counterpart, but half as large, which may be attributed to a larger strain magnitude. We also studied the circulatory characteristics and influence of electron beam radiation. This study provided new physical insights into piezoresistive effects under large strain.

095703

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The initial stages of growth of PTCDA (3,4,9,10 perylene tetracarboxylic dianhydride) at room temperature (RT) on Ge(111)-$c(2\times 8)$ surfaces have been studied by means of scanning tunneling microscopy (STM) under ultrahigh vacuum conditions. The results show that PTCDA molecules have a high mobility at RT on the well ordered areas of the semiconductor substrate, since nucleation is only observed in domain walls, steps and surface defects. However, no molecular ordering has been detected at submonolayer coverage. For higher coverages, the formation of three-dimensional (3D) molecular islands has been observed. These 3D islands present a crystalline nature as demostrated by molecularly resolved STM images. According to these STM measurements, PTCDA molecules are ordered in a herringbone structure, similar to the one observed in PTCDA bulk crystals. Moreover, the 3D crystallites are grown on top of a disordered molecular layer, which acts as a passivating layer.

095704

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The polarity in ZnO nanowires is an important issue since it strongly affects surface configuration and reactivity, nucleation and growth, electro-optical properties, and nanoscale-engineering device performances. However, measuring statistically the polarity of ZnO nanowire arrays grown by chemical bath deposition and elucidating its correlation with the polarity of the underneath polycrystalline ZnO seed layer grown by the sol–gel process represents a major difficulty. To address that issue, we combine resonant x-ray diffraction (XRD) at Zn K-edge using synchrotron radiation with piezoelectric force microscopy and polarity-sensitive chemical etching to statistically investigate the polarity of more than 107 nano-objects both on the macroscopic and local microscopic scales, respectively. By using high temperature annealing under an argon atmosphere, it is shown that the compact, highly c-axis oriented ZnO seed layer is more than 92% Zn-polar and that only a few small O-polar ZnO grains with an amount less than 8% are formed. Correlatively, the resulting ZnO nanowires are also found to be Zn-polar, indicating that their polarity is transferred from the c-axis oriented ZnO grains acting as nucleation sites in the seed layer. These findings pave the way for the development of new strategies to form unipolar ZnO nanowire arrays as a requirement for a number of nanoscale-engineering devices like piezoelectric nanogenerators. They also highlight the great advantage of resonant XRD as a macroscopic, non-destructive method to simultaneously and statistically measure the polarity of ZnO nanowire arrays and of the underneath ZnO seed layer.

095705

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Through scanning tunneling spectroscopy, we envisage imaging a heterostructure, namely a junction formed in a single nanorod. While the differential conductance spectrum provides location of conduction and valence band edges, dI/dV images record energy levels of materials. Such dI/dV images at different voltages allowed us to view p- and n-sections of heterojunction nanorods and more importantly the depletion region in such a junction that has a type-II band alignment. Viewing of selective sections in a heterojunction occurred due to band-bending in the junction and is correlated to the density of states spectrum of the individual semiconductors. The dI/dV images recorded at different voltages could be used to generate a band diagram of a pn junction.

095706

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We elucidate that the tip sharpness in scanning tunneling microscopy (STM) can be characterized through the number of field-emission (FE) resonances. A higher number of FE resonances indicates higher sharpness. We observe empty quantum well (QW) states in Pb islands on Cu(111) under different tip sharpness levels. We found that QW states observed by sharper tips always had lower energies, revealing negative energy shifts. This sharpness-induced energy shift originates from an inhomogeneous electric field in the STM gap. An increase in sharpness increases the electric field inhomogeneity, that is, enhances the electric field near the tip apex, but weakens the electric field near the sample. As a result, higher sharpness can increase the electronic phase in vacuum, causing the lowering of QW state energies. Moreover, the behaviors of negative energy shift as a function of state energy are entirely different for Pb islands with a thickness of two and nine atomic layers. This thickness-dependent behavior results from the electrostatic force in the STM gap decreasing with increasing tip sharpness. The variation of the phase contributed from the expansion deformation induced by the electrostatic force in a nine-layer Pb island is significantly greater, sufficient to effectively negate the increase of electronic phase in vacuum.

095707

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Fe3O4 nanorods coated with nitrogen-doped mesoporous carbon (ND-Fe3O4@mC) shells of defined thicknesses have been prepared via a new microwave-assisted approach. Microstructural characterization of these ND-Fe3O4@mC structures was performed using x-ray diffraction, x-ray photoelectron spectroscopy, transmission electron microscopy, and scanning electron microscopy. Following identification, the electrochemical performance of the catalysts was evaluated using linear sweep voltammetry with a rotating disc electrode system. The present investigation reveals enhanced oxygen reduction reaction catalytic activity and the carbon layer thickness influences oxygen diffusion to the active Fe3O4 nanorod core.

095708

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Further development of microelectronics requires novel or improved technological approaches for device nanofabrication and functional properties characterization. In this paper, we studied the crystal structure and magnetic properties of epitaxial Co nanostrips with the average width of 32.6, 45.3, and 62.6 nm grown on a step-bunched Si(111)5.55 × 5.55-Cu/Cu surface. Technological conditions, under which the ultra-high aspect ratio (∼104) structurally solid, straight nanostrips of hcp-Co with crystallographic axis [0001] oriented along their long side can be grown, were determined. The dependence of the coercive force on the width of the nanostrips was demonstrated. Magnetization reversal through the transverse domain-wall nucleation and propagation in a Co nanostrip was defined with an analytical approach based on the Stoner–Wohlfarth model. Using the first-order reversal curve method, we analyzed the effect of nanostrip uniformity degree on magnetic behavior and the influence of the magnetostatic interactions on the coercive force of individual nanostrips.

095709

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Arrays of multisegmented Co/Au nanowires with designed segment lengths and diameters have been prepared by electrodeposition into aluminum oxide templates. The high quality of the Co/Au interface and the crystallographic structure of Co segments have determined by high-resolution transmission electron microscopy. Magnetic hysteresis loop measurements show larger coercivity and squareness of multisegmented nanowires as compared to single segment Co nanowires. The complementary micromagnetic simulations are in good agreement with the experimental results, confirming that the magnetic behavior is defined mainly by magnetostatic coupling between different segments. The proposed structure constitutes an innovative route towards a 3D array of synchronized magnetic nano-oscillators with large potential in nanoelectronics.

095710

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A multi-functional polymer–carbon nanotube (CNT) nanocable with a hierarchical structure is fabricated by grafting poly (glycidyl methacrylate) (PGMA) from the CNT surface via activators regenerated by electron transfer atom transfer radical polymerization. Multiple CNTs are arranged in parallel in the fabricated nanocable and exhibit strong binding force with sheathing PGMA. In situ mechanical and electrical tests conducted on an individual nanocable reveal its high flexibility and excellent surface insulation, with an electrical resistance of approximately 1 GΩ. On increasing the voltage to the nanocable's electrical breakdown point, nanoscale electrical trees are observed. Such degradation behavior is discussed in the wider context of breakdown mechanisms in polymer based CNTs.

095711

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Multimodal nano-imaging in electrochemical environments is important across many areas of science and technology. Here, scanning electrochemical microscopy (SECM) using an atomic force microscope (AFM) platform with a nanoelectrode probe is reported. In combination with PeakForce tapping AFM mode, the simultaneous characterization of surface topography, quantitative nanomechanics, nanoelectronic properties, and electrochemical activity is demonstrated. The nanoelectrode probe is coated with dielectric materials and has an exposed conical Pt tip apex of ∼200 nm in height and of ∼25 nm in end-tip radius. These characteristic dimensions permit sub-100 nm spatial resolution for electrochemical imaging. With this nanoelectrode probe we have extended AFM-based nanoelectrical measurements to liquid environments. Experimental data and numerical simulations are used to understand the response of the nanoelectrode probe. With PeakForce SECM, we successfully characterized a surface defect on a highly-oriented pyrolytic graphite electrode showing correlated topographical, electrochemical and nanomechanical information at the highest AFM-SECM resolution. The SECM nanoelectrode also enabled the measurement of heterogeneous electrical conductivity of electrode surfaces in liquid. These studies extend the basic understanding of heterogeneity on graphite/graphene surfaces for electrochemical applications.