Background: Sensors that are sensitive to volatile organic compounds, and thus able to monitor the conservation state of food, are precious because they work non-destructively and allow avoiding direct contact with the food, ensuring hygienic conditions. In particular, the monitoring of rancidity would solve a widespread issue in food storage. Results: The sensor discussed here is produced utilizing a novel three-dimensional arrangement of graphene, which is grown on a crystalline silicon carbide wafer previously porousified by chemical etching. This approach allows a very high surface-to-volume ratio. Furthermore, the structure of the sensor surface features a large number of edges, dangling bounds, and active sites, which make the sensor, on a chemically robust skeleton, chemically active, particularly to hydrogenated molecules. The interaction of the sensor with such compounds is read out by measuring the sensor resistance in a four-wire configuration. The sensor performance has been assessed on three hazelnut samples: sound, spoiled, and stink bug hazelnuts. A resistance variation of about ?R = 0.13 ± 0.02 ? between sound and damaged hazelnuts has been detected. Conclusions: Our measurements confirm the ability of the sensor to discriminate between sound and damaged hazelnuts. The sensor signal is stable for days, providing the possibility to use this sensor for the monitoring of the storage state of fats and foods in general. © 2023 Society of Chemical Industry. © 2023 Society of Chemical Industry.

We investigate a ballistic InSb nanoflag-based Josephson junction with Nb superconducting contacts. The high transparency of the superconductor-semiconductor interfaces enables the exploration of quantum transport with parallel short and long conducting channels. Under microwave irradiation, we observe half-integer Shapiro steps that are robust to temperature, suggesting their possible nonequilibrium origin. Our results demonstrate the potential of ballistic InSb nanoflags Josephson junctions as a valuable platform for understanding the physics of hybrid devices and investigating their nonequilibrium dynamics. © 2023 authors. Published by the American Physical Society.

Spatially-resolved organic functionalization of monolayer graphene with 1,3-dipolar cycloaddition of azomethine ylide is successfully achieved using low-energy electron beam irradiation. Indeed, the modification of the graphene honeycomb lattice obtained via electron beam irradiation yields a local increase of the graphene chemical reactivity. As a consequence, thanks to the high-spatially resolved generation of structural defects (similar to 100 nm), a chemical reactivity pattern has been designed over the graphene surface in a well-controlled way. Atomic force microscopy allows to investigate the two-dimensional spatial distribution of the structural defects and Raman spectroscopy reveals the new features that arise from the 1,3-dipolar cycloaddition, confirming the spatial selectivity of the graphene functionalization achieved via defect engineering. The Raman signature of the functionalized graphene is investigated both experimentally and via ab initio molecular dynamics simulations, computing the power spectrum. Furthermore, the organic functionalization is shown to be reversible thanks to the desorption of the azomethine ylide induced by focused laser irradiation. The selective and reversible functionalization of high quality graphene using 1,3-dipolar cycloaddition is a pivotal step for the design and realization of highly complex graphene-based devices and sensors at the nanoscale.

The use of a novel three-dimensional graphene structure allows circumventing the limitations of the two-dimensional nature of graphene and its application in hydrogen absorption. Here we investigate hydrogen -bonding on monolayer graphene conformally grown via the epitaxial growth method on the (0001) face of a porousified 4H-SiC wafer. Hydrogen absorption is studied via Thermal Desorption Spectroscopy (TDS), exposing the samples to either atomic (D) or molecular (D2) deuterium. The graphene growth temperature, hydrogen exposure temperature, and the morphology of the structure are investigated and related to their effect on hydrogen absorption. The three-dimensional graphene structures chemically bind atomic deuterium when exposed to D2. This is the first report of such an event in unfunctionalized graphene-based materials and implies the presence of a catalytic splitting mechanism. It is further shown that the three-dimensional dendritic structure of the porous material temporarily retains the desorbed molecules and causes delayed emission. The capability of chemisorbing atoms after a catalytic splitting of hydrogen, coupled to its large surface-to-volume ratio, make these structures a promising substrate for hydrogen storage devices.

We present a study on the influence of strain-relieving InAlAs buffer layers on metamorphic InAs/InGaAs quantum wells grown by molecular beam epitaxy on GaAs. Residual strain in the buffer layer, the InGaAs barrier and the InAs wells were assessed by X-ray diffraction and high-resolution transmission electron microscopy. By carefully choosing the composition profile and thicknesses of the buffer layer, virtually unstrained InGaAs barriers embedding an InAs quantum well with thickness up to 7 nm can be grown. This allows reaching low-temperature electron mobilities much higher than previously reported for samples obtained by metamorphic growth on GaAs, and comparable to the values achieved for samples grown on InP substrates.

Hydrogen spillover and storage for single-site metal catalysts, including single-atom catalysts (SACs) and single nanocluster catalysts, have been elucidated for various supports but remain poorly understood for inert carbon supports. Here, we use synchrotron-radiation-based methods to investigate the role of single-site Ti catalysts on graphene for hydrogen spillover and storage. Our in situ angle-resolved photoemission spectra results demonstrate a band gap opening, and X-ray absorption spectra reveal the formation of C-H bonds, both indicating partial graphene hydrogenation. With increasing Ti deposition and H-2 exposure, the Ti atoms tend to aggregate to form nanocluster catalysts and yield 13.5% sp(3)-hybridized carbon atoms corresponding to a hydrogen-storage capacity of 1.11 wt % (excluding the weight of the Ti nanoclusters [Bhowmick, R. et al. J. Am. Chem. Soc.2011, 133 (14), 5580]). Our results demonstrate how a simple spillover process at Ti SACs can lead to covalent hydrogen bonding on graphene, thereby providing a strategy for the rational design of carbon-supported single-site catalysts.

Nanometric metallic stripes allow the transmission of optical signals via the excitation and propagation of surface-localized evanescent electromagnetic waves, with important applications in the field of nano-photonics. Whereas this kind of plasmonic phenomena typically exploits noble metals, like Ag or Au, other materials can exhibit viable light-transport efficiency. In this work, we demonstrate the transport of visible light in nanometric niobium stripes coupled with a dielectric polymeric layer, exploiting the remotely-excited/detected Raman signal of black phosphorus (bP) as the probe. The light-transport mechanism is ascribed to the generation of surface plasmon polaritons at the Nb/polymer interface. The propagation length is limited due to the lossy nature of niobium in the optical range, but this material may allow the exploitation of specific functionalities that are absent in noble-metal counterparts.

We report nonreciprocal dissipation-less transport in single ballistic InSb nanoflag Josephson junctions. Applying an in-plane magnetic field, we observe an inequality in supercurrent for the two opposite current propagation directions. Thus, these devices can work as Josephson diodes, with dissipation-less current flowing in only one direction. For small fields, the supercurrent asymmetry increases linearly with external field, and then it saturates as the Zeeman energy becomes relevant, before it finally decreases to zero at higher fields. The effect is maximum when the in-plane field is perpendicular to the current vector, which identifies Rashba spin-orbit coupling as the main symmetry-breaking mechanism. While a variation in carrier concentration in these high-quality InSb nanoflags does not significantly influence the supercurrent asymmetry, it is instead strongly suppressed by an increase in temperature. Our experimental findings are consistent with a model for ballistic short junctions and show that the diode effect is intrinsic to this material.

We theoretically investigate the mapping of the supercurrent distribution in a planar superconductor-normal-superconductor junction in the presence of a perpendicular magnetic field via the scanning gate microscopy technique. We find that the distribution of counterpropagating supercurrents aligned in Josephson vortices can be mapped by the change in the critical current induced by the tip of the scanning probe if the flux in the junction is set close to the maxima of the Fraunhofer pattern. Instead, when the magnetic field drives the junction to a supercurrent minimum in the Fraunhofer pattern, the superconducting phase adapts, and the tip always increases the supercurrent. The perpendicular magnetic field leads to the formation of Josephson vortices, whose extension for highly transparent junctions depends on the current circulation direction. We show that this leads to an asymmetric supercurrent distribution in the junction and that this can be revealed by scanning gate microscopy. We explain our findings on the basis of numerical calculations for both short- and long-junction limits and provide a phenomenological model for the observed phenomena.

Setting up strong Josephson coupling in van der Waals materials in close proximity to superconductors offers several opportunities both to inspect fundamental physics and to develop cryogenic quantum technologies. Here we show evidence of Josephson coupling in a planar few-layer black phosphorus junction. The planar geometry allows us to probe the junction behavior by means of external gates, at different carrier concentrations. Clear signatures of Josephson coupling are demonstrated by measuring supercurrent flow through the junction at milli-Kelvin temperatures. Manifestation of a Fraunhofer pattern with a transverse magnetic field is also reported, confirming the Josephson coupling. These findings represent evidence of proximity Josephson coupling in a planar junction based on a van der Waals material beyond graphene and will expedite further studies, exploiting the peculiar properties of exfoliated black phosphorus thin flakes.

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Organic functionalization of graphene is successfully performed via 1,3-dipolar cycloaddition of azomethine ylide in the liquid phase. The comparison between 1-methyl-2-pyrrolidinone and N,N-dimethylformamide as dispersant solvents, and between sonication and homogenization as dispersion techniques, proves N,N-dimethylformamide and homogenization as the most effective choice. The functionalization of graphene nanosheets and reduced graphene oxide is confirmed using different techniques. Among them, energy-dispersive X-ray spectroscopy allows to map the pyrrolidine ring of the azomethine ylide on the surface of functionalized graphene, while micro-Raman spectroscopy detects new features arising from the functionalization, which are described in agreement with the power spectrum obtained from ab initio molecular dynamics simulation. Moreover, X-ray photoemission spectroscopy of functionalized graphene allows the quantitative elemental analysis and the estimation of the surface coverage, showing a higher degree of functionalization for reduced graphene oxide. This more reactive behavior originates from the localization of partial charges on its surface due to the presence of oxygen defects, as shown by the simulation of the electrostatic features. Functionalization of graphene using 1,3-dipolar cycloaddition is shown to be a significant step towards the controlled synthesis of graphene-based complex structures and devices at the nanoscale.

The quantum Hall (QH) effect represents a unique playground where quantum coherence of electrons can be exploited for various applications, from metrology to quantum computation. In the fractional regime, it also hosts anyons, emergent quasiparticles that are neither bosons nor fermions and possess fractional statistics. Their detection and manipulation represent key milestones in view of topologically protected quantum computation schemes. Exploiting the high degree of phase coherence, edge states in the QH regime have been investigated by designing and constructing electronic interferometers, able to reveal the coherence and statistical properties of the interfering constituents. Here, we review the two main geometries developed in the QH regime, the Mach-Zehnder and the Fabry-Pérot interferometers. We present their basic working principles, fabrication methods and the main results obtained in both the integer and the fractional QH regimes. We will also show how recent technological advances led to the direct experimental demonstration of fractional statistics for Laughlin quasiparticles in a Fabry-Pérot interferometric setup.

High-quality heteroepitaxial two-dimensional (2D) InSb layers are very difficult to realize because of the large lattice mismatch with other widespread semiconductor substrates. A way around this problem is to grow free-standing 2D InSb nanostructures on nanowire (NW) stems, thanks to the capability of NWs to efficiently relax elastic strain along the sidewalls when lattice-mismatched semiconductor systems are integrated. In this work, we optimize the morphology of free-standing 2D InSb nanoflags (NFs). In particular, robust NW stems, optimized growth parameters, and the use of reflection high-energy electron diffraction (RHEED) to precisely orient the substrate for preferential growth are implemented to increase the lateral size of the 2D InSb NFs. Transmission electron microscopy (TEM) analysis of these NFs reveals defect-free zinc blend crystal structure, stoichiometric composition, and relaxed lattice parameters. The resulting NFs are large enough to fabricate Hall-bar contacts with suitable length-to-width ratio enabling precise electrical characterization. An electron mobility of ~29 »500 cm2/(V s) is measured, which is the highest value reported for free-standing 2D InSb nanostructures in literature. We envision the use of 2D InSb NFs for fabrication of advanced quantum devices.

We study surface charge transfer doping of exfoliated black phosphorus (bP) flakes by copper using scanning tunneling microscopy (STM) and spectroscopy (STS) at room temperature. The tunneling spectra reveal a gap in correspondence of Cu islands, which is tentatively attributed to Coulomb blockade phenomena. Moreover, using line spectroscopic measurements across small copper islands, we exploit the potential of the local investigation, showing that the n-type doping effect of copper on bP is short-ranged. These experimental results are substantiated by first-principles simulations, which quantify the role of cluster size for an effective n-type doping of bP and show an electronic decoupling of the topmost bP layer from the underlying layers driven by the copper cluster, consistent with the Coulomb blockade interpretation. Our results provide novel understanding--difficult to retrieve by transport measurements--of the doping of bP by copper, which appears promising for the implementation of ultrasharp p-n junctions in bP.

We demonstrate a programmable quantum Hall circuit that implements an iterative voltage bisection scheme and allows any binary fraction (k/2(n)) of the fundamental resistance quantum R-K/2 = h/2e(2) to be obtained. The circuit requires a number n of bisection stages that only scales logarithmically with the resolution of the set of possible output fractions. The value of k can be set to any integer between 1 and 2(n) by proper and easily predictable gate configuration. The architecture exploits gate-controlled routing, mixing, and equilibration of edge modes of robust quantum Hall states. The device does not contain internal Ohmic contacts and is thus naturally robust towards stray-resistance effects. Our scheme offers an alternative way to obtain custom quantum Hall resistance standards, and its potential advantages are discussed. The basic viability of the approach is demonstrated in a proof-of-principle two-stage bisection circuit built on a high-mobility GaAs/(Al, Ga)As heterostructure operating at a temperature of 260 mK and a magnetic field of 4.1 T. Our prototype achieves a relative quantization precision of the order of 10(-4), which is limited by the experimental setup rather than by the circuit itself.

Achieving good quality Ohmic contacts to van der Waals materials is a challenge, since at the interface between metal and van der Waals material different conditions can occur, ranging from the presence of a large energy barrier between the two materials to the metallization of the layered material below the contacts. In black phosphorus (bP), a further challenge is its high reactivity to oxygen and moisture, since the presence of uncontrolled oxidation can substantially change the behavior of the contacts. Here we study three of the most commonly used metals as contacts to bP, Chromium, Titanium, and Nickel, and investigate their influence on contact resistance against the variability between different flakes and different samples. We investigate the gate dependence of the current-voltage characteristics of field-effect transistors fabricated with these metals on bP, observing good linearity in the accumulation regime for all metals investigated. Using the transfer length method, from an analysis of ten devices, both at room temperature and at low temperature, Ni results to provide the lowest contact resistance to bP and minimum scattering between different devices. Moreover, we observe that our best devices approach the quantum limit for contact resistance both for Ni and for Ti contacts.

This work reports the first experimental study of graphene transferred on ?-Si3N4(0001)/Si(111). A comprehensive quantitative understanding of the physics of ultrathin Si3N4 as a gate dielectric for graphene-based devices is provided. The Si3N4 film is grown on Si(111) under ultra-high vacuum (UHV) conditions and investigated by scanning tunneling microscopy (STM). Subsequently, a graphene flake is deposited on top of it by a polymer-based transfer technique, and a Hall bar device is fabricated from the graphene flake. STM is employed again to study the graphene flake under UHV conditions after device fabrication and shows that the surface quality is preserved. Electrical transport measurements, carried out at low temperature in magnetic field, reveal back gate modulation of carrier density in the graphene channel and show the occurrence of weak localization. Under these experimental conditions, no leakage current between back gate and graphene channel is detected.

Since its discovery, the environmental instability of exfoliated black phosphorus (2D bP) has emerged as a challenge that hampers its wide application in chemistry, physics, and materials science. Many studies have been carried out to overcome this drawback. Here we show a relevant enhancement of ambient stability in few-layer bP decorated with nickel nanoparticles as compared to pristine bP. In detail, the behavior of the Ni-functionalized material exposed to ambient conditions in the dark is accurately studied by Transmission Electron Microscopy (TEM), Raman Spectroscopy, and high resolution X-ray Photoemission and Absorption Spectroscopy. These techniques provide a morphological and quantitative insight of the oxidation process taking place at the surface of the bP flakes. In the presence of Ni nanoparticles (NPs), the decay time of 2D bP to phosphorus oxides is more than three time slower compared to pristine bP, demonstrating an improved structural stability within twenty months of observation.