Multilayers of so-called 2D van der Waals materials have gained considerable attention as active components of next-generation electronic and optoelectronic technologies, with semiconducting black phosphorus (BP) regarded as one of the most promising systems. The applicability and performance limits of BP in both stand-alone and heterostructure-based multilayer devices are determined by individual flake charge transport properties, which synergistically depend on the number of layers and the strength of interlayer coupling between those. In this work, we study the DC electrical transport characteristics of high-quality BP field-effect devices within a wide range of flake thicknesses at room temperature. The experimental data show a non-trivial increase in conductivity and hole density with a reduced number of layers while maintaining constant field-effect mobility due to the prevalence of electron–phonon scattering. Based on the solution of the 1D Schrödinger–Poisson equation, we find that the observed phenomena are a direct consequence of non-negligible interlayer coupling, which in turn causes a local redistribution of free charge carriers towards the central layers. Our data show that due to the electrostatic conditions at the flake surfaces, a naturally protected 2D hole gas can be encapsulated in flakes as high as 10 nm, which preserves the bulk-like bandgap and effective carrier masses due to the electrostatic environment.

The solid-state synthesis of pure sodium-black phosphorus intercalation compounds (Na-BPICs) has been optimized in bulk for two stoichiometric ratios. Specifically, in-situ X-Ray diffraction (XRD) allowed the precise identification of the optimal temperature range for the formation of Na-BPICs: 94 degrees C-96 degrees C. Moreover, as the undesired formation of Na3P takes place at this very same range, we succeeded in introducing a new synthetic route based on a fast-thermal ball milling implementation that results in the bulk production of BPIC without Na3P in 9 out of 10 cases. Finally, by combining XRD, Raman spectroscopy, and DFT calculations we developed a new structural model for Na-based BPICs showing an increase of BP's unit cell with Na atoms incorporated in every second layer. These results will pave the way for the large-scale synthesis and application of pure BPICs, which are of great interest in fields such as optoelectronics or energy storage.

Amongst the different existing methods to passivate black phosphorus (BP) from environmental degradation, the noncovalent functionalization with perylene diimides (PDI) has been postulated as one of the most promising routes because it allows preserving its electronic properties. This work describes the noncovalent functionalization and outstanding environmental protection of BP with tailor made PDI having peri-amide aromatic side chains, which include phenyl and naphthyl groups, exhibiting a significantly increased molecule-BP interaction. These results are rationalized by density functional theory (DFT) calculations showing that the adsorption energies are mainly governed by van der Waals (vdW) interactions and increase concomitantly with the aromatic character of the side chains. The resulting hybrids are thoroughly characterized showing enhanced ambient and thermal stabilities. Last but not least, hybrid organic-inorganic BP-PDI field effect transistors (FETs) are studied for the first time showing the usefulness of PDI derivatives as efficient passivation layers while obtaining improved values of electron mobilities. These results pave the way for the use of optimized PDIs by molecular engineering to preserve the electronic properties of BP FETs, using straightforward wet chemical approaches.

AbstractEs wurde eine direkte Quantifizierungsmethode zur systematischen Bestimmung des Funktionalisierungsgrades von kovalent modifiziertem zweidimensionalem (2D) schwarzen Phosphor (BP) mittels Raman‐Spektroskopie durchgeführt. Die erfolgreiche reduktive Methylierung des BP‐Gitters mit unterschiedlichen Funktionalisierungsgraden unter Verwendung von Natrium‐Interkalationsverbindungen wurde mittels31P‐MAS‐Festkörper‐NMR‐Spektroskopie nachgewiesen. Darüber hinaus ergab die Korrelation von31P‐MAS NMR‐Spektroskopie und statistischer Raman‐Spektroskopie (SRS) die erste Methode zur Bestimmung des Funktionalisierungsgrades von BP allein durch die Evaluierung der Intensitätsverhältnisse bestimmter Peaks in den Raman‐Spektren des kovalent modifizierten Materials, ähnlich dem bekanntenID/IG‐Verhältnisses in der Graphen‐Forschung.

A straightforward quantification method to consistently determine the overall functionalization degree of covalently modified two-dimensional (2D) black phosphorus (BP) by Raman spectroscopy has been carried out. Indeed, the successful reductive methylation of the BP lattice using sodium intercalation compounds and exhibiting different functionalization degrees has been demonstrated by 31 P-magic angle spinning (MAS) NMR spectroscopy. Furthermore, the correlation of 31 P-MAS NMR spectroscopy and statistical Raman spectroscopy (SRS) revealed the first method to determine the functionalization degree of BP solely by evaluating the intensities of distinct peaks in the Raman spectra of the covalently modified material, in a similar way to the widely employed ID /IG ratio of graphene research.

Two-dimensional (2D) black phosphorus (BP) represents one of the most appealing 2D materials due to its electronic, optical, and chemical properties. Many strategies have been pursued to face its environmental instability, covalent functionalization being one of the most promising. However, the extremely low functionalization degrees and the limitations in proving the nature of the covalent functionalization still represent challenges in many of these sheet architectures reported to date. Here we shine light on the structural evolution of 2D-BP upon the addition of electrophilic diazonium salts. We demonstrated the absence of covalent functionalization in both the neutral and the reductive routes, observing in the latter case an unexpected interface conversion of BP to red phosphorus (RP), as characterized by Raman, 31P-MAS NMR, and X-ray photoelectron spectroscopies (XPS). Furthermore, thermogravimetric analysis coupled to gas chromatography and mass spectrometry (TG-GC-MS), as well as electron paramagnetic resonance (EPR) gave insights into the potential underlying radical mechanism, suggesting a Sandmeyer-like reaction.

The noncovalent functionalization of two-dimensional black phosphorus (BP) with tailor made perylene diimides (PDI) leads to the efficient passivation of BP field effect transistors (FET). This straightforward wet chemical approach allows to preserve the electronic properties under environmental conditions. More details can be found in article number 2001290 by Gonzalo Abellán, Andreas Hirsch, and co-workers.

AbstractEine chemisch‐reduktive Volumen‐Funktionalisierung von dünnlagigem schwarzem Phosphor (BP) wurde unter Verwendung von BP‐Interkalationsverbindungen entwickelt. Durch effektive reduktive Aktivierung wurde die kovalente Funktionalisierung des geladenen BP mit Alkylhalogeniden erreicht. Die kovalente Funktionalisierung wurde umfassend mit mehreren spektroskopischen Methoden sowie DFT‐Rechnungen nachgewiesen; es liegt ein höherer Funktionalisierungsgrad als bei neutralen Funktionalisierungsreaktionen vor.

We report a straightforward chemical methodology for controlling the thickness of black phosphorus flakes down to the monolayer limit by layer-by-layer oxidation and thinning, using water as solubilizing agent. Moreover, the oxidation process can be stopped at will by two different passivation procedures, namely the non-covalent functionalization with perylene diimide chromophores, which prevents the photooxidation, or by using a protective ionic liquid layer. The obtained flakes preserve their electronic properties as demonstrated by fabricating a BP field-effect transistor (FET). This work paves the way for the preparation of BP devices with controlled thickness.

Group 15 elements in zero oxidation state (P, As, Sb and Bi), also called pnictogens, are rarely used in catalysis due to the difficulties associated in preparing well–structured and stable materials. Here, we report on the synthesis of highly exfoliated, few layer 2D phosphorene and antimonene in zero oxidation state, suspended in an ionic liquid, with the native atoms ready to interact with external reagents while avoiding aerobic or aqueous decomposition pathways, and on their use as efficient catalysts for the alkylation of nucleophiles with esters. The few layer pnictogen material circumvents the extremely harsh reaction conditions associated to previoussuperacid–catalyzed alkylations, by enabling an alternative mechanism on surface, protected from the water and air by the ionic liquid. Thus, the Calkyl–O bond of the ester is selectively activated on the catalytic pnictogen surface with respect to the much more reactive neighboring C–C and C=O bonds, allowing the alkylation of a variety of acid–sensitive organic molecules and giving synthetic relevancy to the use of simple esters as alkylating agents.

Bence G. Márkus, Ferenc Simon, Károly Nagy, Titusz Fehér, Stefan Wild, Gonzalo Abellán, Julio C. Chacón-Torres, Andreas Hirsch, and Frank Hauke Department of Physics, Budapest University of Technology and Economics and MTA-BME Lendület Spintronics Research Group (PROSPIN), P.O. Box 91, H-1521 Budapest, Hungary Department of Chemistry and Pharmacy Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU) D-91054 Erlangen, Germany and Joint Institute of Advanced Materials and Processes (ZMP), D-90762 Fürth, Germany Yachay Tech. University, School of Physical Sciences and Nanotechnology, 100119 Urcuqúı, Ecuador Institut für Experimental Physik, Freie Universität Berlin, Arnimallee 14, D-14195 Berlin, Germany

Characterization of electronic properties of novel materials is of great importance for exploratory materials development and also for the discovery of new correlated phases. As several novel compounds are available in powder form only, contactless methods, which also work on air sensitive samples, are higly desired. We present that the microwave cavity perturbation technique is a versatile tool to study conductivity in such systems. The examples include studies on semiconducting-metallic crossover in carbon nanotubes upon alkali doping, study of vortex motion in the K$_3$C$_{60}$ superconductor, and the characterization of various alkali atom doped phases of black phosphorus.

The puckered surface of black phosphorus represents an ideal substrate for an unconventional arrangement of physisorbed species and the resulting specific two-dimensional chemistry of this system. This opens the way to investigate the chemical and physical properties of locally confined areas of black phosphorus without the necessity for further physical downscaling of the material. We have evaporated TCNQ on top of black phosphorus under over-saturation non-equilibrium conditions in vacuum. The evolution of linear density and height of droplets formed through oxidation during exposure to air was studied time-dependently by scanning-force microscopy. Our study suggests that the TCNQ molecules spontaneously arrange in a thin layer of the order of a few nm height, which, however, is fragmented with a periodicity of about 100 nm. It is shown that within the confined space separating the layer fragments the chemical dynamics of the oxidation process is remarkably different than on a bare black phosphorus surface.

AbstractAntimonene, a novel group 15 two‐dimensional material, is functionalized with a tailormade perylene bisimide through strong van der Waals interactions. The functionalization process leads to a significant quenching of the perylene fluorescence, and surpasses that observed for either graphene or black phosphorus, thus allowing straightforward characterization of the flakes by scanning Raman microscopy. Furthermore, scanning photoelectron microscopy studies and theoretical calculations reveal a remarkable charge‐transfer behavior, being twice that of black phosphorus. Moreover, the excellent stability under environmental conditions of pristine antimonene has been tackled, thus pointing towards the spontaneous formation of a sub‐nanometric oxide passivation layer. DFT calculations revealed that the noncovalent functionalization of antimonene results in a charge‐transfer band gap of 1.1 eV.

Black phosphorus (bP) has emerged as the next member in the graphene inspired two‐dimensional materials family. Its electronic and magnetic properties are studied herein using electron and nuclear magnetic resonance techniques (ESR and NMR) and microwave conductivity measurement. The latter is a unique technique to study conductivity on air sensitive samples. The ESR study indicates the absence of free charge carriers and no sign of paramagnetic defects are found. 31P NMR shows the presence of a characteristic Pake doublet structure due to the interaction between I = 1/2 nuclei. Microwave conductivity shows, in accordance with the ESR results, that black phosphorus behaves as a semiconductor and we identify extrinsic and intrinsic charge carrier contributions to the conductivity and extracted the sizes of the gaps. ESR measurement also yields that bP might find applications as a microwave absorbent.

Herein, we have developed a systematic study on the oxidation and passivation of mechanically exfoliated black phosphorus (BP). We analyzed the strong anisotropic behavior of BP by scanning Raman microscopy providing an accurate method for monitoring the oxidation of BP via statistical Raman spectroscopy. Furthermore, different factors influencing the environmental instability of the BP, i.e., thickness, lateral dimensions or visible light illumination, have been investigated in detail. Finally, we discovered that the degradation of few-layer BP flakes of <10 nm can be suppressed for months by using ionic liquids, paving the way for the development of BP-based technologies.

AbstractBlack phosphorus intercalation compounds (BPICs) with alkali metals (namely: K and Na) have been synthesized in bulk by solid‐state as well as vapor‐phase reactions. By means of a combination of in situ X‐ray diffraction, Raman spectroscopy, and DFT calculations the structural behavior of the BPICs at different intercalation stages has been demonstrated for the first time. Our results provide a glimpse into the very first steps of a new family of intercalation compounds, with a distinct behavior as compared to its graphite analogues (GICs), showing a remarkable structural complexity and a dynamic behavior.