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.

Charge-Transfer Complexes: Halogen-Doped Anthracene as a Case of Study.

Charge transfer (CT) crystals exhibit unique electronic and magnetic properties with interesting applications. We present a rational and easy guide which allows to foresee the effective charge transfer co-crystal production and that is based on the comparison of the frontier molecular orbital (MO) energies of a donor and acceptor couple. For the sake of comparison, theoretical calculations have been carried out by using the cheap and fast PM6 semiempirical Hamiltonian and pure HF/cc-pVTZ level of the theory. The results are then compared with experimental results obtained both by chemical (bromine and iodine were used as the acceptor) and electrochemical doping (exploiting an original experimental set-up by this laboratory: the electrochemical transistor). Infra-red vibrational experimental results and theoretically calculated spectra are compared to assess both the effective donor-acceptor (D/A) charge-transfer and transport mechanism (giant IRAV polaron signature). XPS spectra have been collected (carbon (1 s) and iodine (3d5/2)) signals, yielding further evidence of the effective formation of the CT anthracene:iodine complex.

Measuring thermal conductivity of nanostructures with the 3ωmethod: the need for finite element modeling.

Conventional techniques of measuring thermal transport properties may be unreliable or unwieldy when applied to nanostructures. However, a simple, all-electrical technique is available for all samples featuring high-aspect-ratio: the 3ωmethod. Nonetheless, its usual formulation relies on simple analytical results which may break down in real experimental conditions. In this work we clarify these limits and quantify them via adimensional numbers and present a more accurate, numerical solution to the 3ωproblem based on the Finite Element Method (FEM). Finally, we present a comparison of the two methods on experimental datasets from InAsSb nanostructures with different thermal transport properties, to stress the crucial need of a FEM counterpart to 3ωmeasurements in nanostructures with low thermal conductivity.

Roadmap on thermoelectricity.

The increasing energy demand and the ever more pressing need for clean technologies of energy conversion pose one of the most urgent and complicated issues of our age. Thermoelectricity, namely the direct conversion of waste heat into electricity, is a promising technique based on a long-standing physical phenomenon, which still has not fully developed its potential, mainly due to the low efficiency of the process. In order to improve the thermoelectric performance, a huge effort is being made by physicists, materials scientists and engineers, with the primary aims of better understanding the fundamental issues ruling the improvement of the thermoelectric figure of merit, and finally building the most efficient thermoelectric devices. In this Roadmap an overview is given about the most recent experimental and computational results obtained within the Italian research community on the optimization of composition and morphology of some thermoelectric materials, as well as on the design of thermoelectric and hybrid thermoelectric/photovoltaic devices.

Semiconductor nanowire arrays for optical sensing: a numerical insight on the impact of array periodicity and density.

Recent advances in the nanofabrication and modeling of metasurfaces have shown the potential of these systems in providing unprecedented control over light-matter interactions at the nanoscale, enabling immediate and tangible improvement of features and specifications of photonic devices that are becoming always more crucial in enhancing everyday life quality. In this work, we theoretically demonstrate that metasurfaces made of periodic and non-periodic deterministic assemblies of vertically aligned semiconductor nanowires can be engineered to display a tailored effective optical response and provide a suitable route to realize advanced systems with controlled photonic properties particularly interesting for sensing applications. The metasurfaces investigated in this paper correspond to nanowire arrays that can be experimentally realized exploiting nanolithography and bottom-up nanowire growth methods: the combination of these techniques allow to finely control the position and the physical properties of each individual nanowire in complex arrays. By resorting to numerical simulations, we address the near- and far-field behavior of a nanowire ensemble and we show that the controlled design and arrangement of the nanowires on the substrate may introduce unprecedented oscillations of light reflectance, yielding a metasurface which displays an electromagnetic behavior with great potential for sensing. Finite-difference time-domain numerical simulations are carried out to tailor the nanostructure parameters and systematically engineer the optical response in the VIS-NIR spectral range. By exploiting our computational-methods we set-up a complete procedure to design and test metasurfaces able to behave as functional sensors. These results are especially encouraging in the perspective of developing arrays of epitaxially grown semiconductor nanowires, where the suggested design can be easily implemented during the nanostructure growth, opening the way to fully engineered nanowire-based optical metamaterials.

Impact of electrostatic doping on carrier concentration and mobility in InAs nanowires.

We fabricate dual-gated electric double layer (EDL) field effect transistors based on InAs nanowires gated with an ionic liquid, and we perform electrical transport measurements in the temperature range from room temperature to 4.2 K. By adjusting the spatial distribution of ions inside the ionic liquid employed as gate dielectric, we electrostatically induce doping in the nanostructures under analysis. We extract low-temperature carrier concentration and mobility in very different doping regimes from the analysis of current-voltage characteristics and transconductances measured exploiting global back-gating. In the liquid gate voltage interval from -2 to 2 V, carrier concentration can be enhanced up to two orders of magnitude. Meanwhile, the effect of the ionic accumulation on the nanowire surface turns out to be detrimental to the electron mobility of the semiconductor nanostructure: the electron mobility is quenched irrespectively to the sign of the accumulated ionic species. The reported results shine light on the effective impact on crucial transport parameters of EDL gating in semiconductor nanodevices and they should be considered when designing experiments in which electrostatic doping of semiconductor nanostructures via electrolyte gating is involved.

30°-Twisted Bilayer Graphene Quasicrystals from Chemical Vapor Deposition.

The artificial stacking of atomically thin crystals suffers from intrinsic limitations in terms of control and reproducibility of the relative orientation of exfoliated flakes. This drawback is particularly severe when the properties of the system critically depends on the twist angle, as in the case of the dodecagonal quasicrystal formed by two graphene layers rotated by 30°. Here we show that large-area 30°-rotated bilayer graphene can be grown deterministically by chemical vapor deposition on Cu, eliminating the need of artificial assembly. The quasicrystals are easily transferred to arbitrary substrates and integrated in high-quality hexagonal boron nitride-encapsulated heterostructures, which we process into dual-gated devices exhibiting carrier mobility up to 105 cm2/(V s). From low-temperature magnetotransport, we find that the graphene quasicrystals effectively behave as uncoupled graphene layers, showing 8-fold degenerate quantum Hall states. This result indicates that the Dirac cones replica detected by previous photoemission experiments do not contribute to the electrical transport.

Orbital Tuning of Tunnel Coupling in InAs/InP Nanowire Quantum Dots.

We report results on the control of barrier transparency in InAs/InP nanowire quantum dots via the electrostatic control of the device electron states. Recent works demonstrated that barrier transparency in this class of devices displays a general trend just depending on the total orbital energy of the trapped electrons. We show that a qualitatively different regime is observed at relatively low filling numbers, where tunneling rates are rather controlled by the axial configuration of the electron orbital. Transmission rates versus filling are further modified by acting on the radial configuration of the orbitals by means of electrostatic gating, and the barrier transparency for the various orbitals is found to evolve as expected from numerical simulations. The possibility to exploit this mechanism to achieve a controlled continuous tuning of the tunneling rate of an individual Coulomb blockade resonance is discussed.

Strategy for accurate thermal biasing at the nanoscale.

We analyze the benefits and shortcomings of a thermal control in nanoscale electronic conductors by means of the contact heating scheme. Ideally, this straightforward approach allows one to apply a known thermal bias across nanostructures directly through metallic leads, avoiding conventional substrate intermediation. We show, by using the average noise thermometry and local noise sensing technique in InAs nanowire-based devices, that a nanoscale metallic constriction on a SiO2 substrate acts like a diffusive conductor with negligible electron-phonon relaxation and non-ideal leads. The non-universal impact of the leads on the achieved thermal bias-which depends on their dimensions, shape and material composition-is hard to minimize, but is possible to accurately calibrate in a properly designed nano-device. Our results allow to reduce the issue of the thermal bias calibration to the knowledge of the heater resistance and pave the way for accurate thermoelectric or similar measurements at the nanoscale.

Thermoelectric Conversion at 30 K in InAs/InP Nanowire Quantum Dots.

We demonstrate high-temperature thermoelectric conversion in InAs/InP nanowire quantum dots by taking advantage of their strong electronic confinement. The electrical conductance G and the thermopower S are obtained from charge transport measurements and accurately reproduced with a theoretical model accounting for the multilevel structure of the quantum dot. Notably, our analysis does not rely on the estimate of cotunnelling contributions, since electronic thermal transport is dominated by multilevel heat transport. By taking into account two spin-degenerate energy levels we are able to evaluate the electronic thermal conductance K and investigate the evolution of the electronic figure of merit ZT as a function of the quantum dot configuration and demonstrate ZT ≈ 35 at 30 K, corresponding to an electronic efficiency at maximum power close to the Curzon-Ahlborn limit.

Conductometric Sensing with Individual InAs Nanowires.

In this work, we isolate individual wurtzite InAs nanowires and fabricate electrical contacts at both ends, exploiting the single nanostructures as building blocks to realize two different architectures of conductometric sensors: (a) the nanowire is drop-casted onto-supported by-a SiO2/Si substrate, and (b) the nanowire is suspended at approximately 250 nm from the substrate. We test the source-drain current upon changes in the concentration of humidity, ethanol, and NO2, using synthetic air as a gas carrier, moving a step forward towards mimicking operational environmental conditions. The supported architecture shows higher response in the mid humidity range (50% relative humidity), with shorter response and recovery times and lower detection limit with respect to the suspended nanowire. These experimental pieces of evidence indicate a minor role of the InAs/SiO2 contact area; hence, there is no need for suspended nanostructures to improve the sensing performance. Moreover, the sensing capability of single InAs nanowires for detection of NO2 and ethanol in the ambient atmosphere is reported and discussed.

Controlling the Quality Factor of a Single Acoustic Nanoresonator by Tuning its Morphology.

The mechanical vibrations of individual gold nanodisks nanopatterned on a sapphire substrate are investigated using ultrafast time-resolved optical spectroscopy. The number and characteristics of the detected acoustic modes are found to vary with nanodisk geometry. In particular, their quality factors strongly depend on nanodisk aspect ratio (i.e., diameter over height ratio), reaching a maximal value of ≈70, higher than those previously measured for substrate-supported nano-objects. The peculiarities of the detected acoustic vibrations are confirmed by finite-element simulations, and interpreted as the result of substrate-induced hybridization between the vibrational modes of a nanodisk. The present findings demonstrate novel possibilities for engineering the vibrational modes of nano-objects.

GHz Electroluminescence Modulation in Nanoscale Subwavelength Emitters.

We investigate light emission from nanoscale point-sources obtained in hybrid metal-GaAs nanowires embedding two sharp axial Schottky barriers. Devices are obtained via the formation of Ni-rich metallic alloy regions in the nanostructure body thanks to a technique of controlled thermal annealing of Ni/Au electrodes. In agreement with recent findings, visible-light electroluminescence can be observed upon suitable voltage biasing of the junctions. We investigate the time-resolved emission properties of our devices and demonstrate an electrical modulation of light generation up to 1 GHz. We explore different drive configurations and discuss the intrinsic bottlenecks of the present device architecture. Our results demonstrate a novel technique for the realization of fast subwavelength light sources with possible applications in sensing and microscopy beyond the diffraction limit.

Gate-Tunable Spatial Modulation of Localized Plasmon Resonances.

We demonstrate localization and field-effect spatial control of the plasmon resonance in semiconductor nanostructures, using scattering-type scanning near-field optical microscopy in the mid-infrared region. We adopt InAs nanowires embedding a graded doping profile to modulate the free carrier density along the axial direction. Our near-field measurements have a spatial resolution of 20 nm and demonstrate the presence of a local resonant feature whose position can be controlled by a back-gate bias voltage. In the present implementation, field-effect induces a modulation of the free carrier density profile yielding a spatial shift of the plasmon resonance of the order of 100 nm. We discuss the relevance of our electrically tunable nanoplasmonic architectures in view of innovative optoelectronic devices concepts.

Giant thermovoltage in single InAs nanowire field-effect transistors.

Millivolt range thermovoltage is demonstrated in single InAs nanowire based field effect transistors. Thanks to a buried heating scheme, we drive both a large thermal bias ΔT > 10 K and a strong field-effect modulation of electric conductance on the nanostructures. This allows the precise mapping of the evolution of the Seebeck coefficient S as a function of the gate-controlled conductivity σ between room temperature and 100 K. Based on these experimental data a novel estimate of the electron mobility is given. This value is compared with the result of standard field-effect based mobility estimates and discussed in relation to the effect of charge traps in the devices.

Heat-Driven Iontronic Nanotransistors.

Thermoelectric polyelectrolytes are emerging as ideal material platform for self-powered bio-compatible electronic devices and sensors. However, despite the nanoscale nature of the ionic thermodiffusion processes underlying thermoelectric efficiency boost in polyelectrolytes, to date no evidence for direct probing of ionic diffusion on its relevant length and time scale has been reported. This gap is bridged by developing heat-driven hybrid nanotransistors based on InAs nanowires embedded in thermally biased Na+ -functionalized (poly)ethyleneoxide, where the semiconducting nanostructure acts as a nanoscale probe sensitive to the local arrangement of the ionic species. The impact of ionic thermoelectric gating on the nanodevice electrical response is addressed, investigating the effect of device architecture, bias configuration and frequency of the heat stimulus, and inferring optimal conditions for the heat-driven nanotransistor operation. Microscopic quantities of the polyelectrolyte such as the ionic diffusion coefficient are extracted from the analysis of hysteretic behaviors rising in the nanodevices. The reported experimental platform enables simultaneously the ionic thermodiffusion and nanoscale resolution, providing a framework for direct estimation of polyelectrolytes microscopic parameters. This may open new routes for heat-driven nanoelectronic applications and boost the rational design of next-generation polymer-based thermoelectric materials.

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.

Surface Nano-Patterning for the Bottom-Up Growth of III-V Semiconductor Nanowire Ordered Arrays.

Ordered arrays of vertically aligned semiconductor nanowires are regarded as promising candidates for the realization of all-dielectric metamaterials, artificial electromagnetic materials, whose properties can be engineered to enable new functions and enhanced device performances with respect to naturally existing materials. In this review we account for the recent progresses in substrate nanopatterning methods, strategies and approaches that overall constitute the preliminary step towards the bottom-up growth of arrays of vertically aligned semiconductor nanowires with a controlled location, size and morphology of each nanowire. While we focus specifically on III-V semiconductor nanowires, several concepts, mechanisms and conclusions reported in the manuscript can be invoked and are valid also for different nanowire materials.