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The interaction between two different materials can present novel phenomena that are quite different from the physical properties observed when each material stands alone. Strong electronic correlations, such as magnetism and superconductivity, can be produced as the result of enhanced Coulomb interactions between electrons. Two-dimensional materials are powerful candidates to search for the novel phenomena because of the easiness of arranging them and modifying their properties accordingly. In this work, we report magnetic effects in graphene, a prototypical non-magnetic two-dimensional semi-metal, in the proximity with sulfur, a diamagnetic insulator. In contrast to the well-defined metallic behaviour of clean graphene, an energy gap develops at the Fermi energy for the graphene/sulfur compound with decreasing temperature. This is accompanied by a steep increase of the resistance, a sign change of the slope in the magneto-resistance between high and low fields, and magnetic hysteresis. A possible origin of the observed electronic and magnetic responses is discussed in terms of the onset of low-temperature magnetic ordering. These results provide intriguing insights on the search for novel quantum phases in graphene-based compounds.

Electromagnetic interaction between a sub-wavelength particle (the `probe')and a material surface (the `sample') is studied theoretically. The interactionis shown to be governed by a series of resonances corresponding to surfacepolariton modes localized near the probe. The resonance parameters depend onthe dielectric function and geometry of the probe, as well as the surfacereflectivity of the material. Calculation of such resonances is carried out forseveral types of axisymmetric probes: spherical, spheroidal, and pear-shaped.For spheroids an efficient numerical method is developed, capable of handlingcases of large or strongly momentum-dependent surface reflectivity. Applicationof the method to highly resonant materials such as aluminum oxide (by itself orcovered with graphene) reveals a rich structure of multi-peak spectra andnonmonotonic approach curves, i.e., the probe-sample distance dependence. Thesefeatures also strongly depend on the probe shape and optical constants of themodel. For less resonant materials such as silicon oxide, the dependence isweak, so that the spheroidal model is reliable. The calculations are donewithin the quasistatic approximation with the radiative damping includedperturbatively.

Moiré patterns are periodic superlattice structures that appear when two crystals with a minor lattice mismatch are superimposed. A prominent recent example is that of monolayer graphene placed on a crystal of hexagonal boron nitride. As a result of the moiré pattern superlattice created by this stacking, the electronic band structure of graphene is radically altered, acquiring satellite sub-Dirac cones at the superlattice zone boundaries. To probe the dynamical response of the moiré graphene, we use infrared (IR) nano-imaging to explore propagation of surface plasmons, collective oscillations of electrons coupled to IR light. We show that interband transitions associated with the superlattice mini-bands in concert with free electrons in the Dirac bands produce two additive contributions to composite IR plasmons in graphene moiré superstructures. This novel form of collective modes is likely to be generic to other forms of moiré-forming superlattices, including van der Waals heterostructures.

We report experimental signatures of plasmonic effects due to electron tunneling between adjacent graphene layers. At subnanometer separation, such layers can form either a strongly coupled bilayer graphene with a Bernal stacking or a weakly coupled double-layer graphene with a random stacking order. Effects due to interlayer tunneling dominate in the former case but are negligible in the latter. We found through infrared nanoimaging that bilayer graphene supports plasmons with a higher degree of confinement compared to single- and double-layer graphene, a direct consequence of interlayer tunneling. Moreover, we were able to shut off plasmons in bilayer graphene through gating within a wide voltage range. Theoretical modeling indicates that such a plasmon-off region is directly linked to a gapped insulating state of bilayer graphene, yet another implication of interlayer tunneling. Our work uncovers essential plasmonic properties in bilayer graphene and suggests a possibility to achieve novel plasmonic functionalities in graphene few-layers.

van der Waals heterostructures assembled from atomically thin crystalline layers of diverse two-dimensional solids are emerging as a new paradigm in the physics of materials. We used infrared nanoimaging to study the properties of surface phonon polaritons in a representative van der Waals crystal, hexagonal boron nitride. We launched, detected, and imaged the polaritonic waves in real space and altered their wavelength by varying the number of crystal layers in our specimens. The measured dispersion of polaritonic waves was shown to be governed by the crystal thickness according to a scaling law that persists down to a few atomic layers. Our results are likely to hold true in other polar van der Waals crystals and may lead to new functionalities.

We examine theoretically the signatures of magnetic adatoms in graphene probed by scanning tunneling spectroscopy (STS). When the adatom hybridizes equally with the two graphene sublattices, the broadening of the local adatom level is anomalous and can scale with the cube of the energy. In contrast to ordinary metal surfaces, the adatom local moment can be suppressed by the proximity of the probing scanning tip. We propose that the dependence of the tunneling conductance on the distance between the tip and the adatom can provide a clear signature for the presence of local magnetic moments. We also show that tunneling conductance can distinguish whether the adatom is located on top of a carbon atom or in the center of a honeycomb hexagon.

We present exact analytical and numerical results for the electronic spectra and the Friedel oscillations around a substitutional impurity atom in a graphene lattice. A chemical dopant in graphene introduces changes in the on-site potential as well as in the hopping amplitude. We employ a T-matrix formalism and find that disorder in the hopping introduces additional interference terms around the impurity that can be understood in terms of bound, semi-bound, and unbound processes for the Dirac electrons. These interference effects can be detected by scanning tunneling microscopy. © Europhysics Letters Association.

The time needed for the osseointegration of titanium implants is deemed too long. Moreover, the bacterial colonization of their surfaces is a major cause of failure. Graphene can overcome these issues but its wet transfer onto substrates employs hazardous chemicals limiting the clinical applications. Alternatively, dry transfer technique has been developed, but the biological properties of this technique remain unexplored. Here, a dry transfer technique based on a hot-pressing method allowed to coat titanium substrates with high-quality graphene and coverage area >90% with a single transfer. The graphene-coated titanium is cytocompatible, did not induce cell membrane damage, induced human osteoblast maturation (gene and protein level), and increased the deposition of mineralized matrix compared to titanium alone. Moreover, graphene decreased the formation of biofilms from Streptococcus mutans, Enterococcus faecalis and even from whole saliva on titanium without killing the bacteria. These findings confirm that coating of titanium with graphene via a dry transfer technique is a promising strategy to improve osseointegration and prevent biofilm formation on implants and devices. [ABSTRACT FROM AUTHOR]

The large-scale implementation of 2D material-based membranes is hindered by mechanical stability and mass transport control challenges. This work describes the fabrication, characterisation, and testing of self-standing graphene oxide (GO) membranes cross-linked with oxides such as Fe 2 O 3 , Al 2 O 3 , CaSO 4 , Nb 2 O 5 , and a carbide, SiC. These cross-linking agents enhance the mechanical stability of the membranes and modulate their mass transport properties. The membranes were prepared by casting aqueous suspensions of GO and SiC or oxide powders onto substrates, followed by drying and detachment to yield self-standing films. This method enabled precise control over membrane thickness and the formation of laminated microstructures with interlayer spacings ranging from 0.8 to 1.2 nm. The resulting self-standing membranes, with areas between 0.002 m 2 and 0.090 m 2 and thicknesses from 0.6 μm to 20 μm, exhibit excellent flexibility and retain their chemical and physical integrity during prolonged testing in direct contact with ethanol/water and methanol/water mixtures in both liquid and vapour phases, with stability demonstrated over 24 h and up to three months. Gas permeation and chemical characterisation tests evidence their suitability for gas separation applications. The interactions promoted by the oxides and carbide with the functional groups of GO confer great stability and unique mass transport properties-the Nb 2 O 5 cross-linked membranes present distinct performance characteristics-creating the potential for scalable advancements in cross-linked 2D material membranes for separation technologies.

The coexistence of correlated electron and hole crystals enables the realization of quantum excitonic states, capable of hosting counterflow superfluidity and topological orders with long-range quantum entanglement. Here we report evidence for imbalanced electron-hole crystals in a doped Mott insulator, namely, α-RuCl 3 , through gate-tunable non-invasive van der Waals doping from graphene. Real-space imaging via scanning tunnelling microscopy reveals two distinct charge orderings at the lower and upper Hubbard band energies, whose origin is attributed to the correlation-driven honeycomb hole crystal composed of hole-rich Ru sites and rotational-symmetry-breaking paired electron crystal composed of electron-rich Ru-Ru bonds, respectively. Moreover, a gate-induced transition of electron-hole crystals is directly visualized, further corroborating their nature as correlation-driven charge crystals. The realization and atom-resolved visualization of imbalanced electron-hole crystals in a doped Mott insulator opens new doors in the search for correlated bosonic states within strongly correlated materials., (© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)

We have investigated the lithium capacity of the 2 H phase of niobium sulfide (NbS 2 ) using density functional theory calculations and experiments. Theoretically, this material is found to allow the intercalation of a double layer of Li in between each NbS 2 layer when in equilibrium with metal Li. The resulting specific capacity (340.8 mAh/g for the pristine material, 681.6 mAh/g for oxidized material) can reach more than double the specific capacity of graphite anodes. The presence of various defects leads to an even higher capacity with a partially reversible conversion of the material, indicating that the performance of the anodes is robust with respect to the presence of defects. Experiments in battery prototypes with NbS 2 -based anodes find a first specific capacity of about 1,130 mAh/g, exceeding the theoretical predictions., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Corrosion is one of the major issues for sustainable manufacturing globally. The annual global cost of corrosion is US$2.5 trillion (approximately 3.4% of the world's GDP). The traditional ways of corrosion protection (such as barriers or inhibiting) are either not very effective (in the case of barrier protection) or excessively expensive (inhibiting). Here, we demonstrate a concept of nanoreactors, which are able to controllably release or adsorb protons or hydroxides directly on corrosion sites, hence, selectively regulating the corrosion reactions. A single nanoreactor comprises a nanocompartment wrapped around by a pH-sensing membrane represented, respectively, by a halloysite nanotube and a graphene oxide/polyamine envelope. A nanoreactor response is determined by the change of a signaling pH on a given corrosion site. The nanoreactors are self-assembled and suitable for mass-line production. The concept creates sustainable technology for developing smart anticorrosion coatings, which are nontoxic, selective, and inexpensive.

There is a need to classify and standardize graphene-related materials giving the growing use of this materials industrially. One of the most used and more difficult to classify is graphene oxide (GO). Inconsistent definitions of GO, closely relating it to graphene, are found in the literature and industrial brochures. Hence, although they have very different physicochemical properties and industrial applications, commonly used classifications of graphene and GO definitions are not substantial. Consequently, the lack of regulation and standardization create trust issues among sellers and buyers that impede industrial development and progress. With that in mind, this study offers a critical assessment of 34 commercially available GOs, characterized using a systematic and reliable protocol for accessing their quality. We establish correlations between GO physicochemical properties and its applications leading to rationale for its classification., (© 2023. The Author(s).)

Two-dimensional (2D) materials can roll up, forming stable scrolls under suitable conditions. However, the great diversity of materials and fabrication techniques has resulted in a huge parameter space significantly complicating the theoretical description of scrolls. In this Letter, we describe a universal binding energy of scrolls determined solely by their material parameters, the bending stiffness, and the Hamaker coefficient. Aiming to predict the stability of functionalized scrolls in water solutions, we consider the electrostatic double-layer repulsion force that may overcome the binding energy and flatten the scrolls. Our predictions are represented as comprehensive maps indicating the stable and unstable regions of a rolled-up conformation state in the space of material and external parameters. While focusing mostly on functionalized graphene in this work, our approach is applicable to the whole range of 2D materials able to form scrolls.

Objective: The presence of metallic species around failed implants raises concerns about the stability of titanium alloy (Ti-6Al-4V). Graphene nanocoating on titanium alloy (GN) has promising anti-corrosion properties, but its long-term protective potential and structural stability remains unknown. The objective was to determine GN's anti-corrosion potential and stability over time., Methods: GN and uncoated titanium alloy (Control) were challenged with a highly acidic fluorinated corrosive medium (pH 2.0) for up to 240 days. The samples were periodically tested using potentiodynamic polarization curves, electrochemical impedance spectroscopy and inductively coupled plasma-atomic emission spectroscopy (elemental release). The integrity of samples was determined using Raman spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy and scanning electron microscopy. Statistical analyses were performed with one-sample t-test, paired t-test and one-way ANOVA with Tukey post-hoc test with a pre-set significance level of 5%., Results: There was negligible corrosion and elemental loss on GN. After 240 days of corrosion challenge, the corrosion rate and roughness increased by two and twelve times for the Control whereas remained unchanged for GN. The nanocoating presented remarkably high structural integrity and coverage area (>98%) at all time points tested., Significance: Graphene nanocoating protects titanium alloy from corrosion and dissolution over a long period while maintaining high structural integrity. This coating has promising potential for persistent protection of titanium and potentially other metallic alloys against corrosion., (Copyright © 2021 The Author(s). Published by Elsevier Inc. All rights reserved.)

Materials with thickness ranging from a few nanometers to a single atomic layer present unprecedented opportunities to investigate new phases of matter constrained to the two-dimensional plane. Particle-particle Coulomb interaction is dramatically affected and shaped by the dimensionality reduction, driving well-established solid state theoretical approaches to their limit of applicability. Methodological developments in theoretical modelling and computational algorithms, in close interaction with experiments, led to the discovery of the extraordinary properties of two-dimensional materials, such as high carrier mobility, Dirac cone dispersion and bright exciton luminescence, and inspired new device design paradigms. This review aims to describe the computational techniques used to simulate and predict the optical, electronic and mechanical properties of two-dimensional materials, and to interpret experimental observations. In particular, we discuss in detail the particular challenges arising in the simulation of two-dimensional constrained fermions and quasiparticles, and we offer our perspective on the future directions in this field., (© 2021 IOP Publishing Ltd.)

Titanium implants present 2 major drawbacks-namely, the long time needed for osseointegration and the lack of inherent antimicrobial properties. Surface modifications and coatings to improve biomaterials can lose their integrity and biological potential when exposed to stressful microenvironments. Graphene nanocoating (GN) can be deposited onto actual-size dental and orthopedic implants. It has antiadhesive properties and can enhance bone formation in vivo. However, its ability to maintain structural integrity and quality when challenged by biologically relevant stresses remains largely unknown. GN was produced by chemical vapor deposition and transferred to titanium via a polymer-assisted transfer technique. GN has high inertness and did not increase expression of inflammatory markers by macrophages, even in the presence of lipopolysaccharides. It kept high coverage at the top tercile of tapered dental implant collars after installation and removal from bone substitute and pig maxilla. It also resisted microbiologically influenced corrosion, and it maintained very high coverage area and quality after prolonged exposure to biofilms and their removal by different techniques. Our findings show that GN is unresponsive to harsh and inflammatory environments and that it maintains a promising level of structural integrity on the top tercile of dental implant collars, which is the area highly affected by biofilms during the onset of implant diseases. Our findings open the avenues for the clinical studies required for the use of GN in the development of implants that have higher osteogenic potential and are less prone to implant diseases.

We demonstrate a fabrication procedure of hybrid devices that consist of reduced graphene oxide films supported by porous polymer membranes that host ionic solutions. We find that we can control the thermal radiation from the surface of reduced graphene oxide through a process of electrically driven reversible ionic intercalation. Through a comparative analysis of the structural, chemical, and optical properties of our reduced graphene oxide films, we identify that the dominant mechanism leading to the intercalation-induced reduction of light emission is Pauli blocking of the interband recombination of charge carriers. We inspect the capabilities of our devices to act as a platform for the electrical control of mid-infrared photonics by observing a bias-induced reduction of apparent temperature of hot surfaces visualized through an infrared thermal camera.

A class of compounds sharing the properties of 2D materials and electrolytes, namely 2D electrolytes is described theoretically and demonstrated experimentally. 2D electrolytes dissociate in different solvents, such as water, and become electrically charged. The chemical and physical properties of these compounds can be controlled by external factors, such as pH, temperature, electric permittivity of the medium, and ionic concentration. 2D electrolytes, in analogy with polyelectrolytes, present reversible morphological transitions from 2D to 1D, as a function of pH, due to the interplay of the elastic and Coulomb energies. Since these materials show stimuli-responsive behavior to the environmental conditions, 2D electrolytes can be considered as a novel class of smart materials that expand the functionalities of 2D materials and are promising for applications that require stimuli-responsive demeanor, such as drug delivery, artificial muscles, and energy storage., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

We show that the degree of oxidation of graphene oxide (GO) can be obtained by using a combination of state-of-the-art ab initio computational modeling and X-ray photoemission spectroscopy (XPS). We show that the shift of the XPS C1s peak relative to pristine graphene, ΔEC1s, can be described with high accuracy by ΔEC1s=A(cO-cl)2+E0, where c0 is the oxygen concentration, A=52.3 eV, cl=0.122, and E0=1.22 eV. Our results demonstrate a precise determination of the oxygen content of GO samples.

Graphene oxide (GO) is an oxygenated functionalized form of graphene that has received considerable attention because of its unique physical and chemical properties that are suitable for a large number of industrial applications. Herein, GO is rapidly obtained directly from the oxidation of graphene using an environmentally friendly modified Hummers method. As the starting material consists of graphene flakes, intercalant agents are not needed and the oxidation reaction is enhanced, leading to orders of magnitude reduction in the reaction time compared to the conventional methods of graphite oxidation. With a superior surface area, the graphene flakes are quickly and more homogeneously oxidized since the flakes are exposed at the same extension to the chemical agents, excluding the necessity of sonication to separate the stacked layers of graphite. This strategy shows an alternative approach to quickly producing GO with different degrees of oxidation that can be potentially used in distinct areas ranging from biomedical to energy storage applications.

Two-dimensional superconductor (2DSC) monolayers with non-centrosymmetry exhibit unconventional Ising pair superconductivity and an enhanced upper critical field beyond the Pauli paramagnetic limit, driving intense research interest. However, they are often susceptible to structural disorder and environmental oxidation, which destroy electronic coherence and provide technical challenges in the creation of artificial van der Waals heterostructures (vdWHs) for devices. Herein, we report a general and scalable synthesis of highly crystalline 2DSC monolayers via a mild electrochemical exfoliation method using flexible organic ammonium cations solvated with neutral solvent molecules as co-intercalants. Using NbSe 2 as a model system, we achieved a high yield (>75%) of large-sized single-crystal monolayers up to 300 µm. The as-fabricated, twisted NbSe 2 vdWHs demonstrate high stability, good interfacial properties and a critical current that is modulated by magnetic field when one flux quantum fits to an integer number of moiré cells. Additionally, formulated 2DSC inks can be exploited to fabricate wafer-scale 2D superconducting wire arrays and three-dimensional superconducting composites with desirable morphologies.

Membranes are ubiquitous in nature with primary functions that include adaptive filtering and selective transport of chemical/molecular species. Being critical to cellular functions, they are also fundamental in many areas of science and technology. Of particular importance are the adaptive and programmable membranes that can change their permeability or selectivity depending on the environment. Here, we explore implementation of such biological functions in artificial membranes and demonstrate two-dimensional self-assembled heterostructures of graphene oxide and polyamine macromolecules, forming a network of ionic channels that exhibit regulated permeability of water and monovalent ions. This permeability can be tuned by a change of pH or the presence of certain ions. Unlike traditional membranes, the regulation mechanism reported here relies on specific interactions between the membranes' internal components and ions. This allows fabrication of membranes with programmable, predetermined permeability and selectivity, governed by the choice of components, their conformation and their charging state.

Ferromagnetism and superconductivity are two antagonistic phenomena since ferromagnetic exchange fields tend to destroy singlet Cooper pairs. Reconciliation of these two competing phases has been achieved in vertically stacked heterostructures where these two orders are confined in different layers. However, controllable integration of these two phases in one atomic layer is a longstanding challenge. Here, an interlayer-space-confined chemical design (ICCD) is reported for the synthesis of dilute single-atom-doped TaS 2 molecular superlattice, whereby ferromagnetism is observed in the superconducting TaS 2 layers. The intercalation of 2H-TaS 2 crystal with bulky organic ammonium molecule expands its van der Waals gap for single-atom doping via co-intercalated cobalt ions, resulting in the formation of quasi-monolayer Co-doped TaS 2 superlattices. Isolated Co atoms are decorated in the basal plane of the TaS 2 via substituting the Ta atom or anchoring at a hollow site, wherein the orbital-selected p-d hybridization between Co and neighboring Ta and S atoms induces local magnetic moments with strong ferromagnetic coupling. This ICCD approach can be applied to various metal ions, enabling the synthesis of a series of crystal-size TaS 2 molecular superlattices., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The identification of metal ions and particles in the vicinity of failed implants has raised the concern that biomedical titanium alloys undergo corrosion in healthy and infected tissues. Various surface modifications and coatings have been investigated to prevent the deterioration and biocorrosion of titanium alloys but so far with limited success. Graphene is a cytocompatible atom-thick film made of carbon atoms. It has a very high surface area and can be deposited onto metal objects with complex shapes. As the carbon lattice has a very small pore size, graphene has promising impermeability capacity. Here, we show that graphene coating can effectively protect Ti-6Al-4V from corrosion. Graphene nanocoatings were produced on Ti-6Al-4V grade 5 and 23 discs and subjected to corrosive challenge (0.5M NaCl supplemented with 2-ppm fluoride, pH of 2.0) up to 30 d. The linear polarization resistance curves and electrochemical impedance spectroscopy analysis showed that the graphene-coated samples presented higher corrosion resistance and electrochemical stability at all time points. Moreover, the corrosion rate of the graphene-coated samples was very low and stable (~0.001 mm/y), whereas that of the uncoated controls increased up to 16 and 5 times for grade 5 and 23 (~0.091 mm/y) at the end point, respectively. The surface oxidation, degradation (e.g., crevice defects), and leaching of Ti, Al, and V ions observed in the uncoated controls were prevented by the graphene nanocoating. The Raman mappings confirmed that the graphene nanocoating presented high structural stability and resistance to mechanical stresses and chemical degradation, keeping >99% of coverage after corrosion challenge. Our findings open the avenues for the use of graphene as anticorrosion coatings for metal biomedical alloys and implantable devices.

We clarify that the chemisorption of oxygen atoms at the edges is a key contributor to the frequently observed edge enhancement and spatial non-uniformities of photoluminescence (PL) in WS 2 monolayers. Here we have investigated with momentum- and real-space nanoimaging of the chemical and electronic density inhomogeneity of WS 2 flakes. Our finding from a large panoply of techniques together with density functional theory calculation confirms that the oxygen chemisorption leads to the electron accumulation at the edges. This facilitates the trion dominance of PL at the edges of WS 2 flakes. Our results highlight and unravel the significance of chemisorbed oxygen at the edges in the PL emission and electronic structure of WS 2 , providing a viable path to enhance the performance of transition-metal-dichalcogenide-based devices.

The details of the superconducting to quantum metal transition (SQMT) at T = 0 are an open problem that invokes great interest in the nature of this exotic and unexpected ground state (Ephron et al., 1996; Mason and Kapitulnik, 1999; Chervenak and Valles, 2000). However, the SQMT was not yet investigated in a crystalline 2D superconductor with coexisting and fluctuating quantum orders. Here, we report the observation of a SQMT in 2D ion-gel-gated 1T-TiSe 2 (Li et al., 2016) driven by a magnetic field. A field-induced crossover between Bose quantum metal and vortex quantum creeping with an increasing field is observed. We discuss the interplay between superconducting and CDW fluctuations (discommensurations) and their relation to the anomalous quantum metal (AQM) phase. From our findings, gate-tunable 1T-TiSe 2 emerges as a privileged platform to scrutinize, in a controlled way, the details of the SQMT, the role of coexisting fluctuating orders and, ultimately, to obtain a deeper understanding of the fate of superconductivity in strictly two-dimensional crystals near zero temperature.

Monolayer VSe 2 , featuring both charge density wave and magnetism phenomena, represents a unique van der Waals magnet in the family of metallic 2D transition-metal dichalcogenides (2D-TMDs). Herein, by means of in situ microscopy and spectroscopic techniques, including scanning tunneling microscopy/spectroscopy, synchrotron X-ray and angle-resolved photoemission, and X-ray absorption, direct spectroscopic signatures are established, that identify the metallic 1T-phase and vanadium 3d 1 electronic configuration in monolayer VSe 2 grown on graphite by molecular-beam epitaxy. Element-specific X-ray magnetic circular dichroism, complemented with magnetic susceptibility measurements, further reveals monolayer VSe 2 as a frustrated magnet, with its spins exhibiting subtle correlations, albeit in the absence of a long-range magnetic order down to 2 K and up to a 7 T magnetic field. This observation is attributed to the relative stability of the ferromagnetic and antiferromagnetic ground states, arising from its atomic-scale structural features, such as rotational disorders and edges. The results of this study extend the current understanding of metallic 2D-TMDs in the search for exotic low-dimensional quantum phenomena, and stimulate further theoretical and experimental studies on van der Waals monolayer magnets., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Development of composite polymer/graphene oxide (GO) materials attracts significant attention due to their unique properties. In this work, highly ordered arrays of hollow microchambers made of composite polyelectrolyte/GO multilayers (PEGOMs) are successfully fabricated via layer-by-layer assembly on sacrificial or sustainable templates having imprinted patterns of microwells on their surface. Mechanical and optical properties of PEGOMs are studied by nanoindentation and near-infrared (NIR) absorption spectroscopy. Incorporation of three GO layers in between the polyelectrolyte multilayer stacks increases Young's modulus and critical stress of the microchambers by a factor of 5.6 and 2.6, respectively. Optical density of this PEGOM film is found to decrease gradually from 0.14 at λ = 800 nm to 0.06 at λ = 1500 nm. Remote opening of PEGOM microchambers with NIR laser beam is also demonstrated. One of the possible applications of the developed structures includes micropackaging and delivery systems in biological tissues with remote triggering., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Objective: To evaluate the surface and wettability characteristics and the microbial biofilm interaction of graphene coating on titanium., Methods: Graphene was deposited on titanium (Control) via a liquid-free technique. The transfer was performed once (TiGS), repeated two (TiGD) and five times (TiGV) and characterized by AFM (n=10), Raman spectroscopy (n=10), contact angle and SFE (n=5). Biofilm formation (n=3) to Streptococcus mutans, Enterococcus faecalis, Pseudomonas aeruginosa and Candida albicans was evaluated after 24h by CV assay, CFU, XTT and confocal microscopy. Statistics were performed by one-way Anova, Tukey's tests and Pearson's correlation analysis at a pre-set significance level of 5 %., Results: Raman mappings revealed coverage yield of 82 % for TiGS and ≥99 % for TiGD and TiGV. Both TiGD and TiGV presented FWHM>44cm -1 and I D /I G ratio<0.12, indicating multiple graphene layers and occlusion of defects. The contact angle was significantly higher for TiGD and TiGV (110° and 117°) comparing to the Control (70°). The SFE was lower for TiGD (13.8mN/m) and TiGV (12.1mN/m) comparing to Control (38.3mN/m). TiGD was selected for biofilm assays and exhibited significant reduction in biofilm formation for all microorganisms compared to Control. There were statistical correlations between the high contact angle and low SFE of TiGD and decreased biofilm formation., Significance: TiGD presented high quality and coverage and decreased biofilm formation for all species. The increased hydrophobicity of graphene films was correlated with the decreased biofilm formation for various species., (Copyright © 2018. Published by Elsevier Inc.)

There are hundreds of companies worldwide claiming to produce "graphene," showing a large variation in its properties. A systematic and reliable protocol is developed to test graphene quality using electron microscopy, atomic force microscopy, Raman spectroscopy, elemental analysis, X-ray photoelectron spectrometry, and scanning and transmission electron microscopy, which is used to study graphene from 60 producers. The statistical nature of the liquid-phase exfoliation of graphite is established. It is shown that the current classification of graphene flakes used in the market is erroneous. A new classification is proposed in terms of distribution functions for number of layers and flake size. It is shown unequivocally that the quality of the graphene produced in the world today is rather poor, not optimal for most applications, and most companies are producing graphite microplatelets. This is possibly the main reason for the slow development of graphene applications, which usually require a customized solution in terms of graphene properties. It is argued that the creation of stringent standards for graphene characterization and production, taking into account both the physical properties, as well as the requirements from the particular application, is the only way forward to create a healthy and reliable worldwide graphene market., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Ferroelectric thin film has attracted great interest for nonvolatile memory applications and can be used in either ferroelectric Schottky diodes or ferroelectric tunneling junctions due to its promise of fast switching speed, high on-to-off ratio, and nondestructive readout. Two-dimensional α-phase indium selenide (In 2 Se 3 ), which has a modest band gap and robust ferroelectric properties stabilized by dipole locking, is an excellent candidate for multidirectional piezoelectric and switchable photodiode applications. However, the large-scale synthesis of this material is still elusive, and its performance as a ferroresistive memory junction is rarely reported. Here, we report the low-temperature molecular-beam epitaxy (MBE) of large-area monolayer α-In 2 Se 3 on graphene and demonstrate the use of α-In 2 Se 3 on graphene in ferroelectric Schottky diode junctions by employing high-work-function gold as the top electrode. The polarization-modulated Schottky barrier formed at the interface exhibits a giant electroresistance ratio of 3.9 × 10 6 with a readout current density of >12 A/cm 2 , which is more than 200% higher than the state-of-the-art technology. Our MBE growth method allows a high-quality ultrathin film of In 2 Se 3 to be heteroepitaxially grown on graphene, thereby simplifying the fabrication of high-performance 2D ferroelectric junctions for ferroresistive memory applications.

We report a functional hybrid made of silver nanoparticles (AgNPs) embedded in an amorphous aluminium oxide (alumina) film. This laser-initiated process allows formation of AgNPs and amorphous alumina in localized regions defined by the scanning laser beam. Due to metal enhanced fluorescence, this hybrid exhibits strong blue fluorescence emission under ultraviolet excitation. Upon irradiating with electrons at dosages of 1 to 20 mC cm-2, AgNPs become more metallic while the Al film is further oxidised. As a result, the fluorescing property is intensified. Using a hybrid irradiated with 10 mC cm-2, the electronic conductivity of the sample is improved by 11.5 times compared to that of the as-synthesized hybrid film. Excitation by UV light on the sample results in an increase in the detected current of nearly 29 times. Given that the electron beam patterned message is selectively visible only under UV or blue light irradiation, this hybrid film is thus a possible platform for steganographic transmission.

Molybdenum diselenide (MoSe 2 ) is a promising two-dimensional material for next-generation electronics and optoelectronics. However, its application has been hindered by a lack of large-scale synthesis. Although chemical vapor deposition (CVD) using laboratory furnaces has been applied to grow two-dimensional (2D) MoSe 2 cystals, no continuous film over macroscopically large area has been produced due to the lack of uniform control in these systems. Here, we investigate the molecular beam epitaxy (MBE) of 2D MoSe 2 on hexagonal boron nitride (hBN) substrate, where highly crystalline MoSe 2 film can be grown with electron mobility ∼15 cm 2 /(V s). Scanning transmission electron microscopy (STEM) shows that MoSe 2 grains grown at an optimum temperature of 500 °C are highly oriented and coalesced to form continuous film with predominantly mirror twin boundaries. Our work suggests that van der Waals epitaxy of 2D materials is tolerant of lattice mismatch but is facilitated by substrates with similar symmetry.

The field of valleytronics has promised greater control of electronic and spintronic systems with an additional valley degree of freedom. However, conventional and two-dimensional valleytronic systems pose practical challenges in the utilization of this valley degree of freedom. Here we show experimental evidences of the valley effect in a bulk, ambient, and bias-free model system of Tin(II) sulfide. We elucidate the direct access and identification of different sets of valleys, based primarily on the selectivity in absorption and emission of linearly polarized light by optical reflection/transmission and photoluminescence measurements, and demonstrate strong optical dichroic anisotropy of up to 600% and nominal polarization degrees of up to 96% for the two valleys with band-gap values 1.28 and 1.48 eV, respectively; the ease of valley selection further manifested in their non-degenerate nature. Such discovery enables a new platform for better access and control of valley polarization.

Understanding the local electronic properties of individual defects and dopants in black phosphorus (BP) is of great importance for both fundamental research and technological applications. Here, we employ low-temperature scanning tunnelling microscope (LT-STM) to probe the local electronic structures of single acceptors in BP. We demonstrate that the charge state of individual acceptors can be reversibly switched by controlling the tip-induced band bending. In addition, acceptor-related resonance features in the tunnelling spectra can be attributed to the formation of Rydberg-like bound hole states. The spatial mapping of the quantum bound states shows two distinct shapes evolving from an extended ellipse shape for the 1s ground state to a dumbbell shape for the 2p x excited state. The wave functions of bound hole states can be well-described using the hydrogen-like model with anisotropic effective mass, corroborated by our theoretical calculations. Our findings not only provide new insight into the many-body interactions around single dopants in this anisotropic two-dimensional material but also pave the way to the design of novel quantum devices.

The extreme mechanical resilience of graphene and the peculiar coupling it hosts between lattice and electronic degrees of freedom have spawned a strong impetus toward strain-engineered graphene where, on the one hand, strain augments the richness of its phenomenology and makes possible new concepts for electronic devices, and on the other hand, new and extreme physics might take place. Here, we demonstrate that the shape of substrates supporting graphene sheets can be optimized for approachable experiments where strain-induced pseudomagnetic fields (PMF) can be tailored by pressure for directionally selective electronic transmission and pinching-off of current flow down to the quantum channel limit. The Corbino-type layout explored here furthermore allows filtering of charge carriers according to valley and current direction, which can be used to inject or collect valley-polarized currents, thus realizing one of the basic elements required for valleytronics. Our results are based on a framework developed to realistically determine the combination of strain, external parameters, and geometry optimally compatible with the target spatial profile of a desired physical property-the PMF in this case. Characteristic conductance profiles are analyzed through quantum transport calculations on large graphene devices having the optimal shape.

Two-dimensional black phosphorus (BP) has sparked enormous research interest due to its high carrier mobility, layer-dependent direct bandgap and outstanding in-plane anisotropic properties. BP is one of the few two-dimensional materials where it is possible to tune the bandgap over a wide energy range from the visible up to the infrared. In this article, we report the observation of a giant Stark effect in electrostatically gated few-layer BP. Using low-temperature scanning tunnelling microscopy, we observed that in few-layer BP, when electrons are injected, a monotonic reduction of the bandgap occurs. The injected electrons compensate the existing defect-induced holes and achieve up to 35.5% bandgap modulation in the light-doping regime. When probed by tunnelling spectroscopy, the local density of states in few-layer BP shows characteristic resonance features arising from layer-dependent sub-band structures due to quantum confinement effects. The demonstration of an electrical gate-controlled giant Stark effect in BP paves the way to designing electro-optic modulators and photodetector devices that can be operated in a wide electromagnetic spectral range.

Objective: The objective was to investigate the potential of graphene (Gp) to induce odontogenic and osteogenic differentiation in dental pulp stem cells (DPSC)., Methods: Gp was produced by chemical vapor deposition. DPSC were seeded on Gp or glass (Gl). Cells were maintained in culture medium for 28 days. Every two days, culture medium from Gp was used to treat cells on Gl and vice versa. Mineralization and differentiation of DPSC on all substrates were evaluated after 14 and 28 days by alizarin red S staining, qPCR, immunofluorescence and FACS. Statistics were performed with two-way ANOVA and multiple comparisons were performed using Tukey's post hoc test at a pre-set significance level of 5%., Results: After 14 and 28 days, Gp induced higher levels of mineralization as compared to Gl. Odontoblastic genes (MSX-1, PAX and DMP) were down-regulated and osteogenic genes and proteins (RUNX2, COL and OCN) were significantly upregulated on Gp comparing to Gl (p<0.05 for all cases). Medium from Gp induced downregulation of odontoblastic genes and increased bone-related gene and protein on Gl., Significance: Graphene induced osteogenic and not odontoblastic differentiation of DPSC without the use of chemical inducers for osteogenesis. Graphene has the potential to be used as a substrate for craniofacial bone tissue engineering research., (Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.)

Two-dimensional layered transition-metal dichalcogenides have attracted considerable interest for their unique layer-number-dependent properties. In particular, vertical integration of these two-dimensional crystals to form van der Waals heterostructures can open up a new dimension for the design of functional electronic and optoelectronic devices. Here we report the layer-number-dependent photocurrent generation in graphene/MoS 2 /graphene heterostructures by creating a device with two distinct regions containing one-layer and seven-layer MoS 2 to exclude other extrinsic factors. Photoresponse studies reveal that photoresponsivity in one-layer MoS 2 is surprisingly higher than that in seven-layer MoS 2 by seven times. Spectral-dependent studies further show that the internal quantum efficiency in one-layer MoS 2 can reach a maximum of 65%, far higher than the 7% in seven-layer MoS 2 . Our theoretical modelling shows that asymmetric potential barriers in the top and bottom interfaces of the graphene/one-layer MoS 2 /graphene heterojunction enable asymmetric carrier tunnelling, to generate usually high photoresponsivity in one-layer MoS 2 device.

A high-performance 2D photodetector based on a bilayer structure comprising a WSe2 monolayer and CH3 NH3 PbI3 organolead halide perovskite is reported. High performance is realized by modification of the WSe2 monolayer with laser healing and perovskite functionalization. After modification, the output of the device was three orders of magnitude better than the pristine device; the performance is superior to that of most of the 2D photodetectors based on transition-metal-dichalcogenides (TMDs). This result indicates that combinatory TMDs-halide perovskite hybrids can be promising building blocks in optoelectronics., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Objective: The aim of this study was to evaluate the cytotoxicity and differentiation potential of a graphene oxide (GO)-based substrate using dental pulp stem cell (DPSC)., Methods: GO was obtained via chemical exfoliation of graphite using the modified Hummer's method and dispersed in water-methanol solution. 250μL of 1.5mg/mL solution were added to a cover slip and allowed to dry (25°C, 24h). GO-based substrate was characterized by Raman spectroscopy, AFM and contact angle. DPSC were seeded on GO and glass (control). Cell attachment and proliferation were evaluated by polymeric F-actin staining, SEM and MTS assay for five days. mRNA expression of MSX-1, PAX-9, RUNX2, COL I, DMP-1 and DSPP were evaluated by qPCR (7 and 14 days). Statistical analyses were performed by either Mann-Whitney, one or two-way Anova followed by and Tukey's post hoc analysis (α=0.05)., Results: Peaks at 1587cm(-1) and 1340cm(-1) (G and D band) and ID/IG of 0.83 were observed for GO with Raman. AFM showed that GO was randomly deposited and created a rougher surface comparing to the control. Cells successfully adhered on both substrates. There was no difference in cell proliferation after 5 days. Cells on GO presented higher expression for all genes tested except MSX-1 and RUNX2 for 7 days., Significance: GO-based substrate allowed DPSC attachment, proliferation and increased the expression of several genes that are upregulated in mineral-producing cells. These findings open opportunities to the use of GO alone or in combination with dental materials to improve their bioactivity and beyond., (Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.)

The physics of two-dimensional (2D) materials and heterostructures based on such crystals has been developing extremely fast. With these new materials, truly 2D physics has begun to appear (for instance, the absence of long-range order, 2D excitons, commensurate-incommensurate transition, etc.). Novel heterostructure devices--such as tunneling transistors, resonant tunneling diodes, and light-emitting diodes--are also starting to emerge. Composed from individual 2D crystals, such devices use the properties of those materials to create functionalities that are not accessible in other heterostructures. Here we review the properties of novel 2D crystals and examine how their properties are used in new heterostructure devices., (Copyright © 2016, American Association for the Advancement of Science.)

Black phosphorus has recently emerged as a new layered crystal that, due to its peculiar and anisotropic crystalline and electronic band structures, may have important applications in electronics, optoelectronics and photonics. Despite the fact that the edges of layered crystals host a range of singular properties whose characterization and exploitation are of utmost importance for device development, the edges of black phosphorus remain poorly characterized. In this work, the atomic structure and behaviour of phonons near different black phosphorus edges are experimentally and theoretically studied using Raman spectroscopy and density functional theory calculations. Polarized Raman results show the appearance of new modes at the edges of the sample, and their spectra depend on the atomic structure of the edges (zigzag or armchair). Theoretical simulations confirm that the new modes are due to edge phonon states that are forbidden in the bulk, and originated from the lattice termination rearrangements.

Strongly bound excitons confined in two-dimensional (2D) semiconductors are dipoles with a perfect in-plane orientation. In a vertical stack of semiconducting 2D crystals, such in-plane excitonic dipoles are expected to efficiently couple across van der Waals gap due to strong interlayer Coulomb interaction and exchange their energy. However, previous studies on heterobilayers of group 6 transition metal dichalcogenides (TMDs) found that the exciton decay dynamics is dominated by interlayer charge transfer (CT) processes. Here, we report an experimental observation of fast interlayer energy transfer (ET) in MoSe2/WS2 heterostructures using photoluminescence excitation (PLE) spectroscopy. The temperature dependence of the transfer rates suggests that the ET is Förster-type involving excitons in the WS2 layer resonantly exciting higher-order excitons in the MoSe2 layer. The estimated ET time of the order of 1 ps is among the fastest compared to those reported for other nanostructure hybrid systems such as carbon nanotube bundles. Efficient ET in these systems offers prospects for optical amplification and energy harvesting through intelligent layer engineering.

The relation between unusual Mexican-hat band dispersion, ferromagnetism, and ferroelasticity is investigated using a combination of analytical, first-principles, and phenomenological methods. The class of material with Mexican-hat band edge is studied using the α-SnO monolayer as a prototype. Such a band edge causes a van Hove singularity diverging with 1/sqrt[E], and a charge doping in these bands can lead to time-reversal symmetry breaking. Herein, we show that a material with Mexican-hat band dispersion, α-SnO, can be ferroelastic or paraelastic depending on the number of layers. Also, an unexpected multiferroic phase is obtained in a range of hole density for which the material presents ferromagnetism and ferroelasticity simultaneously.