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Hexagonal boron nitride (hBN) and black phosphorus (bP) are crystalline materials that can be seen as ordered stackings of two-dimensional layers, which lead to outstanding anisotropic physical properties. The knowledge of the thermal equations of state of hBN and bP is of great interest in the field of 2D materials for a better understanding of the anisotropic thermo-mechanical properties and exfoliation mechanism of these materials. Despite several theoretical and experimental studies, important uncertainties remain in the determination of the thermoelastic parameters of hBN and bP. Here, we report accurate thermal expansion and compressibility measurements along the individual crystallographic axes, using in situ high-temperature and high-pressure high-resolution synchrotron X-ray diffraction. In particular, we have quantitatively determined the subtle variations of the in-plane thermo-mechanical parameters by subjecting these materials to hydrostatic pressure conditions and collecting a large number of data points in small pressure and temperature increments. Based on the anisotropic behavior of bP, we propose the use of this material as sensor for the simultaneous determination of pressure and temperature in the range 0-5 GPa, 298-1700 K., Comment: 26 pages, 10 Figures, 7 Tables

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 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 explain the Coulomb blockade by an electronic decoupling of the topmost bP layer from the underlying layers driven by the copper cluster. 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 ultra-sharp p-n junctions in bP.

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 novel 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 Fraunhofer pattern with a transverse magnetic field is also reported, confirming the Josephson coupling. These findings represent the first evidence of proximity Josephson coupling in a planar junction based on a van der Waals material beyond graphene and open the way to new studies, exploiting the peculiar properties of exfoliated black phosphorus thin flakes.

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 TEM (Transmission Electron Microscopy), 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 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.

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. In this study, we investigate the influence of the metal used for the contacts to bP against the variability between different flakes and different samples, using three of the most used metals as contacts: Chromium, Titanium, and Nickel. Using the transfer length method, from an analysis of ten devices, both at room temperature and at low temperature, Ni results to be the best metal for Ohmic contacts to bP, providing the lowest contact resistance and minimum scattering between different devices. Moreover, we investigate the gate dependence of the current-voltage characteristics of these devices. In the accumulation regime, we observe good linearity for all metals investigated., Comment: 30 pages, 4 figures

Phosphorene, the 2D material derived from black phosphorus, has recently attracted a lot of interest for its properties, suitable for applications in material science. In particular, the physical features and the prominent chemical reactivity on its surface render this nanolayered substrate particularly promising for electrical and optoelectronic applications. In addition, being a new potential ligand for metals, it opens the way for a new role of the inorganic chemistry in the 2D world, with special reference to the field of catalysis. The aim of this review is to summarize the state of the art in this subject and to present our most recent results in preparation, functionalization and use of phosphorene and its decorated derivatives. In particular, we discuss several key points, which are currently under investigation: the synthesis, the characterization by theoretical calculations, the high pressure behaviour of black phosphorus, as well as decoration with nanoparticles and encapsulation in polymers. Finally, device fabrication and electrical transport measurements are overviewed on the basis of recent literature and new results collected in our laboratories.

The burgeoning interest in 2D black phosphorus (bP) contributes to expand its applications in countless fields. In the present study, 2D bP is used as a support for homogeneously dispersed palladium nanoparticles directly grown on it by a wet chemical process. EELS-STEM analysis evidences a strong interaction between palladium and P atoms of bP nanosheets. A quantitative evaluation of this interaction comes from XAS measurements that find out a very short Pd-P distance of 2.26 {\AA} proving for the first time the existence of an unprecedented Pd-P coordination bond of covalent nature. Additionally, the average Pd-P coordination number of about 1.7 reveals that bP acts as a polydentate phosphine ligand towards the surface Pd atoms of the nanoparticles, thus preventing their agglomeration and inferring structural stability. These unique properties result in a superior performance in the catalytic hydrogenation of chloronitroarenes to chloroaniline, where a higher chemoselectivity in comparison to other heterogeneous catalyst based on palladium has been observed.

Resistivity measurements of a few-layer black phosphorus (bP) crystal in parallel magnetic fields up to 45 T are reported as a function of the angle between the in-plane field and the source-drain (S-D) axis of the device. The crystallographic directions of the bP crystal were determined by Raman spectroscopy, with the zigzag axis found within 5{\deg} of the S-D axis, and the armchair axis in the orthogonal planar direction. A transverse magneto-resistance (TMR) as well as a classically-forbidden longitudinal magneto-resistance (LMR) are observed. Both are found to be strongly anisotropic and non-monotonic with increasing in-plane field. Surprisingly, the relative magnitude (in %) of the positive LMR is larger than the TMR above $\sim$32 T. Considering the known anisotropy of bP whose zigzag and armchair effective masses differ by a factor of approximately seven, our experiment strongly suggests this LMR to be a consequence of the anisotropic Fermi surface of bP., Comment: 12 pages, 8 figures

Black phosphorus (bP) has been recently investigated for next generation nanoelectronic multifunctional devices. However, the intrinsic instability of exfoliated bP (the bP nanoflakes) towards both moisture and air has so far overshadowed its practical implementation. In order to contribute to fill this gap, we report here the preparation of new hybrid polymer-based materials where bP nanoflakes exhibit a significantly improved stability. The new materials have been prepared by different synthetic paths including: i) the mixing of conventionally liquid-phase exfoliated bP (in DMSO) with PMMA solution; ii) the direct exfoliation of bP in a polymeric solution; iii) the in situ radical polymerization after exfoliating bP in the liquid monomer (methyl methacrylate, MMA). This last methodology concerns the preparation of stable suspensions of bPn-MMA by sonication-assisted liquid phase exfoliation (LPE) of bP in the presence of MMA followed by radical polymerization. The hybrids characteristics have been compared in order to evaluate the bP dispersion and the effectiveness of the bPn interfacial interactions with polymer chains aimed at their long-term environmental stabilization. The passivation of bPn results particularly effective when the hybrid material is prepared by in situ polymerization. By using this synthetic methodology, the nanoflakes, even if with a gradient of dispersion (size of aggregates), preserve their chemical structure from oxidation (as proved by both Raman and 31P-Solid State NMR studies) and are particularly stable to air and UV light exposure.

Hybrid materials, containing a 2D filler embedded in a polymeric matrix, are an interesting platform for several applications, because of the variety of properties that the filler can impart to the polymer matrix when dispersed at the nanoscale. Moreover, novel properties could arise from the interaction between the two. Mostly the bulk properties of these materials have been studied so far, especially focusing on how the filler changes the polymeric matrix properties. Here we propose a complete change of perspective by using the hybrid nanocomposite material as a platform suitable to engineer the properties of the filler and to exploit its potential in the fabrication of devices. As a proof of concept of the versatility and potentiality of the new method, we applied this approach to prepare black phosphorus nanocomposites through its dispersion in poly (methyl methacrylate). Black phosphorus is a very interesting 2D material, whose application have so far been limited by its very high reactivity to oxygen and water. In this respect, we show that electronic-grade black phosphorus flakes, already embedded in a protecting matrix since their exfoliation from the bulk material, are endowed with significant increased stability, and can be further processed into devices without degrading their properties.

Polystyrene-based phosphorene nanocomposites were prepared by a solvent blending procedure allowing the embedding of black phosphorus (BP) nanoflakes in the polymer matrix. Raman spectroscopy, X Ray Diffraction and TEM microscopy were employed to characterize the structural and the morphological characteristics of the achieved hybrids, with the aim to evaluate the dispersion level of black phosphorus layers. TGA, DSC analysis as well as thermal oxidation and photo-degradation techniques were employed to investigate the thermal- and the photo-stability of the samples. The collected results evidenced better thermal and photostability of both polymer matrix and dispersed layered phosphorus, suggesting really interesting polymer-nanofiller synergic effects ascribable to the presence and the good dispersion of the 2D-nanomaterial., Comment: 14 pages, 6 figures

Nickel nanoparticles were dispersed on the surface of exfoliated black phosphorus and the resulting nanohybrid Ni/2DBP showed an improved stability respect to pristine 2D BP when kept in ambient conditions in the darkness. Ni/2DBP was applied as catalyst in the semihydrogenation of phenylacetylene and exhibited high conversion and selectivity towards styrene. These features were preserved after recycling tests revealing the high stability of the nanohybrid., Comment: Corrected misspelled author name

Water is believed to be harmful for the stability of phosphorene.On the contrary, the presence of small amount of water allows the synthesis of high-quality material in liquid exfoliation of black phosphorus using dimethylsulfoxide as solvent. A phosphorus/water molar ratio between 1.5 and 14 maximizes the quality of the phosphorene flakes and their stability.