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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 (3d 5/2 )) signals, yielding further evidence of the effective formation of the CT anthracene:iodine complex., (© 2024 Wiley-VCH GmbH.)

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 d I /d V branch dispersion, revealing a giant, strongly anisotropic g -factor in excess of 60 (100) for the radial (tilted) field configurations.

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 3 ω method. 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 3 ω problem 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 3 ω measurements in nanostructures with low thermal conductivity., (Creative Commons Attribution license.)

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., (Creative Commons Attribution license.)

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., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

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.

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.

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.

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., (© 2021 IOP Publishing Ltd.)

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.

The thermo-mechanical properties of streptavidin-conjugated gold nanospheres, adhered to a surface via complex molecular chains, are investigated by two-color infrared asynchronous optical sampling pump-probe spectroscopy. Nanospheres with different surface densities have been deposited and exposed to a plasma treatment to modify their polymer binding chains. The aim is to monitor their optical response in complex chemical environments that may be experienced in, e.g., photothermal therapy or drug delivery applications. By applying unsupervised learning techniques to the spectroscopic traces, we identify their thermo-mechanical response variation. This variation discriminates nanospheres in different chemical environments or different surface densities. Such discrimination is not evident based on a standard analysis of the spectroscopic traces. This kind of analysis is important, given the widespread application of conjugated gold nanospheres in medicine and biology.

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 SiO 2 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.

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 SnO 2 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.

Graphene oxide (GO) is an important carbon nanomaterial (NM) that has been used, but limited literature is available regarding the impacts induced in aquatic organisms by this pollutant and, in particular in invertebrate species. The polychaete Diopatra neapolitana has frequently been used to evaluate the effects of environmental disturbances in estuarine systems due to its ecological and socio-economic importance but to our knowledge no information is available on D. neapolitana physiological and biochemical alterations due to GO exposure. Thus, the present study aimed to assess the toxic effects of different concentrations of GO (0.01; 0.10 and 1.00mg/L) in D. neapolitana physiological (regenerative capacity) and biochemical (energy reserves, metabolic activity and oxidative stress related biomarkers) performance, after 28days of exposure. The results obtained revealed that the exposure to GO induced negative effects on the regenerative capacity of D. neapolitana, with organisms exposed to higher concentrations regenerating less segments and taking longer periods to completely regenerate. GO also seemed to alter energy-related responses, especially glycogen content, with higher values in polychaetes exposed to GO which may result from a decreased metabolism (measured by electron transport system activity), when exposed to GO. Furthermore, under GO contamination D. neapolitana presented cellular damage, despite higher activities of antioxidant and biotransformation enzymes in individuals exposed to GO., (Copyright © 2017 Elsevier Inc. All rights reserved.)