Spin-Resolved Magneto-Tunneling and Giant Anisotropic g-Factor in Broken Gap InAs-GaSb Core-Shell Nanowires.

We experimentally and computationally investigate the magneto-conductance across the radial heterojunction of InAs-GaSb core-shell nanowires under a magnetic field, B, up to 30 T and at temperatures in the range 4.2-200 K. The observed double-peak negative differential conductance markedly blue-shifts with increasing B. The doublet accounts for spin-polarized currents through the Zeeman split channels of the InAs (GaSb) conduction (valence) band and exhibits strong anisotropy with respect to B orientation and marked temperature dependence. Envelope function approximation and a semiclassical (WKB) approach allow to compute the magnetic quantum states of InAs and GaSb sections of the nanowire and to estimate the B-dependent tunneling current across the broken-gap interface. Disentangling different magneto-transport channels and a thermally activated valence-to-valence band transport current, we extract the g-factor from the spin-up and spin-down dI/dV branch dispersion, revealing a giant, strongly anisotropic g-factor in excess of 60 (100) for the radial (tilted) field configurations.

Electrochemical exfoliation of graphite in H2SO4, Li2SO4 and NaClO4 solutions monitored in situ by Raman microscopy and spectroscopy.

The electrochemical exfoliation of graphite is one of the cheapest and most tunable industrial techniques to produce graphene nanosheets with a tunable degree of oxidation and solubility. Anodic oxidation allows high-yield production of electrochemically exfoliated graphene oxide (EGO) in either acid or salt solutions, with the key role played by ions electrochemically driven in between the graphene sheets. This chemical intercalation is followed by a mesoscale mechanical exfoliation process, which is key for the high yield of the process, but which is still poorly understood. In this work, we use Raman spectroscopy to simultaneously monitor the intercalation and oxidation processes taking place on the surface of highly ordered pyrolytic graphite (HOPG) during electrochemical exfoliation. The mechanism of EGO formation in either acidic (0.5 M H2SO4) or neutral (0.5 M Li2SO4) electrolytes through blistering and cracking steps is discussed and described. This process is also compared to the non-destructive intercalation of graphite in an organic electrolyte (1 M NaClO4 in acetonitrile). The results obtained show how high exfoliation yield and low defectivity can be achieved by the combination of efficient, non-destructive intercalation followed by chemical decomposition of the intercalants and gas production.

Gate-Switchable Molecular Diffusion on a Graphene Field-Effect Transistor.

Controlling the surface diffusion of particles on 2D devices creates opportunities for advancing microscopic processes such as nanoassembly, thin-film growth, and catalysis. Here, we demonstrate the ability to control the diffusion of F4TCNQ molecules at the surface of clean graphene field-effect transistors (FETs) via electrostatic gating. Tuning the back-gate voltage (VG) of a graphene FET switches molecular adsorbates between negative and neutral charge states, leading to dramatic changes in their diffusion properties. Scanning tunneling microscopy measurements reveal that the diffusivity of neutral molecules decreases rapidly with a decreasing VG and involves rotational diffusion processes. The molecular diffusivity of negatively charged molecules, on the other hand, remains nearly constant over a wide range of applied VG values and is dominated by purely translational processes. First-principles density functional theory calculations confirm that the energy landscapes experienced by neutral vs charged molecules lead to diffusion behavior consistent with experiment. Gate-tunability of the diffusion barrier for F4TCNQ molecules on graphene enables graphene FETs to act as diffusion switches.

Functionalization of reduced graphite oxide sheets with a zwitterionic surfactant.

Films of a few layers in thickness of reduced graphite oxide (RGO) sheets functionalized by the zwitterionic surfactant N-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (DDPS) are obtained by using the Langmuir-Blodgett method. The quality of the RGO sheets is checked by analyzing the degrees of reduction and defect repair by means of X-ray photoelectron spectroscopy, atomic force microscopy (AFM), field-emission scanning electron microscopy (SEM), micro-Raman spectroscopy, and electrical conductivity measurements. A modified Hummers method is used to obtain highly oxidized graphite oxide (GO) together with a centrifugation-based method to improve the quality of GO. The GO samples are reduced by hydrazine or vitamin C. Functionalization of RGO with the zwitterionic surfactant improves the degrees of reduction and defect repair of the two reducing agents and significantly increases the electrical conductivity of paperlike films compared with those prepared from unfunctionalized RGO.

Polarization Control in Integrated Silicon Waveguides Using Semiconductor Nanowires.

In this work, we show the design of a silicon photonic-based polarization converting device based on the integration of semiconduction InP nanowires on the silicon photonic platform. We present a comprehensive numerical analysis showing that full polarization conversion (from quasi-TE modes to quasi-TM modes, and vice versa) can be achieved in devices exhibiting small footprints (total device lengths below 20 µm) with minimal power loss (<2 dB). The approach described in this work can pave the way to the realization of complex and re-configurable photonic processors based on the manipulation of the state of polarization of guided light beams.

Polarization Control in Integrated Graphene-Silicon Quantum Photonics Waveguides.

We numerically investigated the use of graphene nanoribbons placed on top of silicon-on-insulator (SOI) strip waveguides for light polarization control in silicon photonic-integrated waveguides. We found that two factors mainly affected the polarization control: the graphene chemical potential and the geometrical parameters of the waveguide, such as the waveguide and nanoribbon widths and distance. We show that the graphene chemical potential influences both TE and TM polarizations almost in the same way, while the waveguide width tapering enables both TE-pass and TM-pass polarizing functionalities. Overall, by increasing the oxide spacer thickness between the silicon waveguide and the top graphene layer, the device insertion losses can be reduced, while preserving a high polarization extinction ratio.

3D Multi-Branched SnO2 Semiconductor Nanostructures as Optical Waveguides.

Nanostructures with complex geometry have gathered interest recently due to some unusual and exotic properties associated with both their shape and material. 3D multi-branched SnO2 one-dimensional nanostructrures, characterized by a "node"-i.e., the location where two or more branches originate, are the ideal platform to distribute signals of different natures. In this work, we study how this particular geometrical configuration affects light propagation when a light source (i.e., laser) is focused onto it. Combining scanning electron microscopy (SEM) and optical analysis along with Raman and Rayleigh scattering upon illumination, we were able to understand, in more detail, the mechanism behind the light-coupling occurring at the node. Our experimental findings show that multi-branched semiconductor 1D structures have great potential as optically active nanostructures with waveguiding properties, thus paving the way for their application as novel building blocks for optical communication networks.

Strong Modulations of Optical Reflectance in Tapered Core-Shell Nanowires.

Random assemblies of vertically aligned core-shell GaAs-AlGaAs nanowires displayed an optical response dominated by strong oscillations of the reflected light as a function of the incident angle. In particular, angle-resolved specular reflectance measurements showed the occurrence of periodic modulations in the polarization-resolved spectra of reflected light for a surprisingly wide range of incident angles. Numerical simulations allowed for identifying the geometrical features of the core-shell nanowires leading to the observed oscillatory effects in terms of core and shell thickness as well as the tapering of the nanostructure. The present results indicate that randomly displaced ensembles of nanoscale heterostructures made of III-V semiconductors can operate as optical metamirrors, with potential for sensing applications.

Self-Assembled InAs Nanowires as Optical Reflectors.

Subwavelength nanostructured surfaces are realized with self-assembled vertically-aligned InAs nanowires, and their functionalities as optical reflectors are investigated. In our system, polarization-resolved specular reflectance displays strong modulations as a function of incident photon energy and angle. An effective-medium model allows one to rationalize the experimental findings in the long wavelength regime, whereas numerical simulations fully reproduce the experimental outcomes in the entire frequency range. The impact of the refractive index of the medium surrounding the nanostructure assembly on the reflectance was estimated. In view of the present results, sensing schemes compatible with microfluidic technologies and routes to innovative nanowire-based optical elements are discussed.

Electrochemical Functionalization of Graphene at the Nanoscale with Self-Assembling Diazonium Salts.

We describe a fast and versatile method to functionalize high-quality graphene with organic molecules by exploiting the synergistic effect of supramolecular and covalent chemistry. With this goal, we designed and synthesized molecules comprising a long aliphatic chain and an aryl diazonium salt. Thanks to the long chain, these molecules physisorb from solution onto CVD graphene or bulk graphite, self-assembling in an ordered monolayer. The sample is successively transferred into an aqueous electrolyte, to block any reorganization or desorption of the monolayer. An electrochemical impulse is used to transform the diazonium group into a radical capable of grafting covalently to the substrate and transforming the physisorption into a covalent chemisorption. During covalent grafting in water, the molecules retain the ordered packing formed upon self-assembly. Our two-step approach is characterized by the independent control over the processes of immobilization of molecules on the substrate and their covalent tethering, enabling fast (t < 10 s) covalent functionalization of graphene. This strategy is highly versatile and works with many carbon-based materials including graphene deposited on silicon, plastic, and quartz as well as highly oriented pyrolytic graphite.

Tuning electronic transport in cobalt-filled carbon nanotubes using magnetic fields.

Metal-filled and decorated carbon nanotubes represent a class of quasi one-dimensional hybrid systems with enormous potential for applications in nanoelectronics and spintronics. Here we show that is possible to control the electrical conduction in ferromagnetic metal-filled carbon nanotubes by means of external magnetic fields, suggesting specific dimensionality-dependent conduction regimes. By increasing the magnetic field, we drive the charge flow from a positive to a negative magneto-conductance, revealing channel-selective conduction. Furthermore, the zero-field current temperature dependence shows different regimes, suggesting that the inter-shell hopping, assisted by the cobalt clusters, plays a key role in the dimensional crossover. The possibility of engineering and controlling the nature and size of the conducting shells and the filling with magnetic materials can allow the implementation of these systems in tunable hybrid nano-sensors and multifunctional magnetic devices.

Synergic Exfoliation of Graphene with Organic Molecules and Inorganic Ions for the Electrochemical Production of Flexible Electrodes.

A facile and efficient method based on electrochemistry for the production of graphene-based materials for electronics is demonstrated. Uncharged acetonitrile molecules are intercalated in graphite by electrochemical treatment, owing to the synergic action of perchlorate ions dissolved in acetonitrile. Then, acetonitrile molecules are decomposed with microwave irradiation, which causes gas production and rapid graphite exfoliation, with an increase in the graphite volume of up to 600 %. Upon further processing and purification, highly dispersible nanosheets are obtained that can be processed into thin layers by roll-to-roll transfer or into thicker electrodes with excellent capacitance stability upon extensive charging/discharging cycles. The good exfoliation yield (>50 % of monolayers), minimal oxidation damage and good electrochemical stability of the nanosheets obtained were confirmed by scanning force and electron microscopy, as well as Raman spectroscopy and galvanostatic analyses.

Metal-filled carbon nanotubes as a novel class of photothermal nanomaterials.

Metal-filled carbon nanotubes represent a novel class of photothermal nanomaterials: when illuminated by visible light they exhibit a strong enhancement of the temperature at the metal sites, due to the enhanced plasmonic light absorption at the metal surface, which behaves as a heat radiator. Potential applications include nanomedicine, heat-assisted magnetic recording, and light-activated thermal gradient-driven devices.

Magneto-transport of graphene and quantum phase transitions in the quantum Hall regime.

In this paper we show the electronic transport and the quantum phase transitions that characterize the quantum Hall regime in graphene placed on SiO(2) substrates at magnetic fields up to 28 T and temperatures down to 4 K. The analysis of the temperature dependence of the Hall and longitudinal resistivity reveals intriguing non-universalities of the critical exponents of the plateau-insulator transition. These exponents depend on the type of disorder that governs the electrical transport and its characterization is important for the design and fabrication of novel graphene nano-devices.

Cobalt nanocluster-filled carbon nanotube arrays: engineered photonic bandgap and optical reflectivity.

Perfect vertically aligned and periodically arranged arrays of multidielectric heterostructures are ideal platforms both for photonic crystals and photonic bandgap materials. Carbon nanotubes grown inside anodic alumina templates form a novel class of heterostructured materials ideally suited for building such platforms. By engineering metallic (cobalt) nanoclusters inside the nanotubes, we present a novel method for tailoring the photonic bandgap as well as the magnitude of the reflectivity in these systems. We present spectroscopic ellipsometry (SE) and reflectivity measurements to investigate the effect of the presence of cobalt clusters on the optical response of multiwall carbon nanotubes (MWNT) grown in anodized alumina template. The real (ε(1)) and imaginary (ε(2)) part of the pseudodielectric function of the MWNT and Co-MWNT system have been studied in a wide energy range (1.4-5 eV). We found that the cobalt filling modifies the electronic structure of the nanotubes, suggesting that the insertion of the clusters leads to a semiconductor behavior. Angle-resolved reflectivity measurements further show that the metal filling drastically enhances the optical response up to 2 orders of magnitude.