Fatigue Response of MoS2 with Controlled Introduction of Atomic Vacancies.

Fatigue-induced failure resulting from repetitive stress-strain cycles is a critical concern in the development of robust and durable nanoelectromechanical devices founded on 2D semiconductors. Defects, such as vacancies and grain boundaries, inherent in scalable materials can act as stress concentrators and accelerate fatigue fracture. Here, we investigate MoS2 with controlled atomic vacancies, to elucidate its mechanical reliability and fatigue response as a function of atomic defect density. High-quality MoS2 demonstrates an exceptional fatigue response, enduring 109 cycles at 80% of its breaking strength (13.5 GPa), surpassing the fatigue resistance of steel and approaching that of graphene. The introduction of atomic defect densities akin to those generated during scalable synthesis processes (∼1012 cm-2) reduces the fatigue strength to half the breaking strength. Our findings also point toward a sudden defect reconfiguration prior to global failure as the primary fatigue mechanism, offering valuable insights into structure-property relationships.

Ultralarge Free-Standing Imine-Based Covalent Organic Framework Membranes Fabricated via Compression.

Demand continues for processing methods to shape covalent organic frameworks (COFs) into macroscopic objects that are needed for their practical applications. Herein, a simple compression method to prepare large-scale, free-standing homogeneous and porous imine-based COF-membranes with dimensions in the centimeter range and excellent mechanical properties is reported. This method entails the compression of imine-based COF-aerogels, which undergo a morphological change from an elastic to plastic material. The COF-membranes fabricated upon compression show good performances for the separation of gas mixtures of industrial interest, N2 /CO2 and CH4 /CO2 . It is believed that the new procedure paves the way to a broader range of COF-membranes.

Exfoliation of Alpha-Germanium: A Covalent Diamond-Like Structure.

2D materials have opened a new field in materials science with outstanding scientific and technological impact. A largely explored route for the preparation of 2D materials is the exfoliation of layered crystals with weak forces between their layers. However, its application to covalent crystals remains elusive. Herein, a further step is taken by introducing the exfoliation of germanium, a narrow-bandgap semiconductor presenting a 3D diamond-like structure with strong covalent bonds. Pure α-germanium is exfoliated following a simple one-step procedure assisted by wet ball-milling, allowing gram-scale fabrication of high-quality layers with large lateral dimensions and nanometer thicknesses. The generated flakes are thoroughly characterized by different techniques, giving evidence that the new 2D material exhibits bandgaps that depend on both the crystallographic direction and the number of layers. Besides potential technological applications, this work is also of interest for the search of 2D materials with new properties.

Confined Crack Propagation in MoS2 Monolayers by Creating Atomic Vacancies.

In two-dimensional crystals, fractures propagate easily, thus restricting their mechanical reliability. This work demonstrates that controlled defect creation constitutes an effective approach to avoid catastrophic failure in MoS2 monolayers. A systematic study of fracture mechanics in MoS2 monolayers as a function of the density of atomic vacancies, created by ion irradiation, is reported. Pristine and irradiated materials were studied by atomic force microscopy, high-resolution scanning transmission electron microscopy, and Raman spectroscopy. By inducing ruptures through nanoindentations, we determine the strength and length of the propagated cracks within MoS2 atom-thick membranes as a function of the density and type of the atomic vacancies. We find that a 0.15% atomic vacancy induces a decrease of 40% in strength with respect to that of pristine samples. In contrast, while tear holes in pristine 2D membranes span several microns, they are restricted to a few nanometers in the presence of atomic and nanometer-sized vacancies, thus increasing the material's fracture toughness.

Improved Graphene Blisters by Ultrahigh Pressure Sealing.

Graphene is a very attractive material for nanomechanical devices and membrane applications. Graphene blisters based on silicon oxide microcavities are a simple but relevant example of nanoactuators. A drawback of this experimental setup is that gas leakage through the graphene-SiO2 interface contributes significantly to the total leak rate. Here, we study the diffusion of air from pressurized graphene drumheads on SiO2 microcavities and propose a straightforward method to improve the already strong adhesion between graphene and the underlying SiO2 substrate, resulting in reduced leak rates. This is carried out by applying controlled and localized ultrahigh pressure (>10 GPa) with an atomic force microscopy diamond tip. With this procedure, we are able to significantly approach the graphene layer to the SiO2 surface around the drumheads, thus enhancing the interaction between them, allowing us to better seal the graphene-SiO2 interface, which is reflected in up to ∼ 4 times lower leakage rates. Our work opens an easy way to improve the performance of graphene as a gas membrane on a technological relevant substrate such as SiO2.

Customized MFM probes based on magnetic nanorods.

Focused Electron Beam Induced Deposition (FEBID) for magnetic tip fabrication is presented in this work as an alternative to conventional sputtering-based Magnetic Force Microscopy (MFM) tips. FEBID enables the growth of a high-aspect-ratio magnetic nanorod with customized geometry and composition to overcome the key technical limitations of MFM probes currently on the market. The biggest advantage of these tips, in comparison with CoCr coated pyramidal probes, lies in the capability of creating sharp ends, nearly 10 nm in diameter, which provides remarkable (topographic and magnetic) lateral resolution in samples with magnetic features close to the resolution limits of the MFM technique itself. The shape of the nanorods produces a very confined magnetic stray field, whose interaction with the sample is extremely localized and perpendicular to the surface, with negligible in-plane components. This effect can lead to a better analytical and numerical modelling of the MFM probes and to an increase in the sensitivity without perturbing the magnetic configuration of soft samples. Besides, the high-aspect ratio achievable in FEBID nanorod tips makes them magnetically harder than the commercial ones, reaching coercive fields higher than 900 Oe. According to the results shown, tips based on magnetic nanorods grown by FEBID can be eventually used for quantitative analysis in MFM measurements. Moreover, the customized growth of Co- or Fe-based tips onto levers with different mechanical properties allows MFM studies that demand different measuring conditions. To showcase the versatility of this type of probe, as a last step, MFM is performed in a liquid environment, which still remains a challenge for the MFM community largely due to the lack of appropriate probes on the market. This opens up new possibilities in the investigation of magnetic biological samples.

Multifunctional carbon nanotubes covalently coated with imine-based covalent organic frameworks: exploring structure-property relationships through nanomechanics.

The assembly of 3-dimensional covalent organic frameworks on the surface of carbon nanotubes is designed and successfully developed for the first time via the hybridization of imine-based covalent organic frameworks (COF-300) and oxidized MWCNTs by one-pot chemical synthesis. The resulting hybrid material ox-MWCNTs@COF exhibits a conformal structure that consists of a uniform amorphous COF layer covering the ox-MWCNT surface. The measurements of individual hybrid nanotube mechanical strength performed with atomic force microscopy provide insights into their stability and resistance. The results evidence a very robust hybrid tubular nanostructure that preserves the benefits obtained from COF, such as CO2 adsorption. Further digestion of the organic structure with aniline enables the study of the interplay between the hybrid interface and its nanomechanics. This new hybrid nanomaterial presents exceptional mechanical and electrical properties, merging the properties of the CNT template and COF-300.

AFM Manipulation of Gold Nanowires To Build Electrical Circuits.

We introduce scanning-probe-assisted nanowire circuitry (SPANC) as a new method to fabricate electrodes for the characterization of electrical transport properties at the nanoscale. SPANC uses an atomic force microscope (AFM) to manipulate nanowires to create complex and highly conductive nanostructures (paths) that work as nanoelectrodes, allowing connectivity and electrical characterization of other nano-objects. The paths are formed by the spontaneous cold welding of gold nanowires upon mechanical contact, leading to an excellent contact resistance of ∼9 Ω/junction. SPANC is an easy to use and cost-effective technique that fabricates clean nanodevices. Hence, this new method can complement and/or be an alternative to other well-established methods to fabricate nanocircuits such as electron beam lithography (EBL). The circuits made by SPANC are easily reconfigurable, and their fabrication does not require the use of polymers and chemicals. In this work, we present a few examples that illustrate the capabilities of this method, allowing robust device fabrication and electrical characterization of several nano-objects with sizes down to ∼10 nm, well below the current smallest size able to be contacted in a device using the standard available technology (∼30 nm). Importantly, we also provide the first experimental determination of the sheet resistance of thin antimonene flakes.

One-Pot Preparation of Mechanically Robust, Transparent, Highly Conductive, and Memristive Metal-Organic Ultrathin Film.

The future of 2D flexible electronics relies on the preparation of conducting ultrathin films of materials with mechanical robustness and flexibility in a simple but controlled manner. In this respect, metal-organic compounds present advantages over inorganic laminar crystals owing to their structural, chemical, and functional diversity. While most metal-organic compounds are usually prepared in bulk, recent work has shown that some of them are processable down to low dimensional forms. Here we report the one-pot preparation, carried out at the water-air interface, of ultrathin (down to 4 nm) films of the metal-organic compound [Cu2I2(TAA)] n (TAA= thioacetamide). The films are shown to be homogeneous over mm2 areas, smooth, highly transparent, mechanically robust, and good electrical conductors with memristive behavior at low frequencies. This combination of properties, as well as the industrial availability of the two building blocks required for the preparation, demonstrates their wide range potential in future flexible and transparent electronics.

High-Resolution Atomic Force Microscopy Imaging of Nucleic Acids.

Exploring the limits of spatial resolution has been a constant in the history of atomic force microscopy imaging. Since its invention in 1986, the AFM has beaten the barrier of resolution continuously, thanks to technical developments, miniaturization of tips, and implementation of new imaging modes. The double helix structure of DNA has been always at the horizon of resolution. Today, this milestone has been reached, not only imaging DNA but also its close relative double-stranded RNA. Here, we provide a comprehensive description of the methods employed and the steps required to image the helical periodicity of these two nucleic acids with the sample immersed in a buffer solution.

High Electrical Conductivity of Single Metal-Organic Chains.

Molecular wires are essential components for future nanoscale electronics. However, the preparation of individual long conductive molecules is still a challenge. MMX metal-organic polymers are quasi-1D sequences of single halide atoms (X) bridging subunits with two metal ions (MM) connected by organic ligands. They are excellent electrical conductors as bulk macroscopic crystals and as nanoribbons. However, according to theoretical calculations, the electrical conductance found in the experiments should be even higher. Here, a novel and simple drop-casting procedure to isolate bundles of few to single MMX chains is demonstrated. Furthermore, an exponential dependence of the electrical resistance of one or two MMX chains as a function of their length that does not agree with predictions based on their theoretical band structure is reported. This dependence is attributed to strong Anderson localization originated by structural defects. Theoretical modeling confirms that the current is limited by structural defects, mainly vacancies of iodine atoms, through which the current is constrained to flow. Nevertheless, measurable electrical transport along distances beyond 250 nm surpasses that of all other molecular wires reported so far. This work places in perspective the role of defects in 1D wires and their importance for molecular electronics.

Recent progress in 2D group-VA semiconductors: from theory to experiment.

Phosphorene, an emerging two-dimensional material, has received considerable attention due to its layer-controlled direct bandgap, high carrier mobility, negative Poisson's ratio and unique in-plane anisotropy. As cousins of phosphorene, 2D group-VA arsenene, antimonene and bismuthene have also garnered tremendous interest due to their intriguing structures and fascinating electronic properties. 2D group-VA family members are opening up brand-new opportunities for their multifunctional applications encompassing electronics, optoelectronics, topological spintronics, thermoelectrics, sensors, Li- or Na-batteries. In this review, we extensively explore the latest theoretical and experimental progress made in the fundamental properties, fabrications and applications of 2D group-VA materials, and offer perspectives and challenges for the future of this emerging field.

Recent Progress on Antimonene: A New Bidimensional Material.

Antimonene, defined in sensu stricto as a single layer of antimony atoms, is recently the focus of numerous theoretical works predicting a variety of interesting properties and is quickly attracting the attention of the scientific community. However, what places antimonene in a different category from other 2D crystals is its strong spin-orbit coupling and a drastic evolution of its properties from the monolayer to the few-layer system. The recent isolation of this novel 2D material pushes the interest for antimonene even further. Here, a review of both theoretical predictions and experimental results is compiled. First, an account of the calculations anticipating an electronic band structure suitable for optoelectronics and thermoelectric applications in monolayer form and a topological semimetal in few-layer form is given. Second, the different approaches to produce antimonene-mechanical and liquid phase exfoliation, and epitaxial growth methods-are reviewed. In addition, this work also reports the main characterization techniques used to study this exotic material. This review provides insights for further exploring the appealing properties of antimonene and puts forward the opportunities and challenges for future applications from (opto)electronic device fabrication to biomedicine.

Noncovalent Functionalization and Charge Transfer in Antimonene.

Antimonene, 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.

Formation of Conductive DNA-Based Nanowires via Conjugation of dsDNA with Cationic Peptide.

A novel conductive DNA-based nanomaterial, DNA-peptide wire, composed of a DNA core and a peripheral peptide layer, is presented. The electrical conductivity of the wire is found to be at least three orders in magnitude higher than that of native double-stranded DNA (dsDNA). High conductivity of the wires along with a better resistance to mechanical deformations caused by interactions between the substrate and electrode surface make them appealing for a wide variety of nanoelectronic and biosensor applications.

Few-Layer Antimonene by Liquid-Phase Exfoliation.

We report on a fast and simple method to produce highly stable isopropanol/water (4:1) suspensions of few-layer antimonene by liquid-phase exfoliation of antimony crystals in a process that is assisted by sonication but does not require the addition of any surfactant. This straightforward method generates dispersions of few-layer antimonene suitable for on-surface isolation. Analysis by atomic force microscopy, scanning transmission electron microscopy, and electron energy loss spectroscopy confirmed the formation of high-quality few-layer antimonene nanosheets with large lateral dimensions. These nanolayers are extremely stable under ambient conditions. Their Raman signals are strongly thickness-dependent, which was rationalized by means of density functional theory calculations.

Antimonene: Mechanical Isolation of Highly Stable Antimonene under Ambient Conditions (Adv. Mater. 30/2016).

On page 6332, J. Gómez-Herrero, F. Zamora, and co-workers describe the isolation of antimonene, a new allotrope of antimony that consists of a single layer of atoms. They obtain antimonene flakes by the scotch tape method; these flakes are highly stable in ambient conditions and even when immersed in water. The 1.2 eV gap calculated in this study suggests potential applications in optoelectronics.

Mechanical Isolation of Highly Stable Antimonene under Ambient Conditions.

Antimonene fabricated by mechanical exfoliation is highly stable under atmospheric conditions over periods of months and even when immersed in water. Density functional theory confirms the experiments and predicts an electronic gap of ≈1 eV. These results highlight the use of antimonene for optoelectronics applications.

High resolution atomic force microscopy of double-stranded RNA.

Double-stranded (ds) RNA mediates the suppression of specific gene expression, it is the genetic material of a number of viruses, and a key activator of the innate immune response against viral infections. The ever increasing list of roles played by dsRNA in the cell and its potential biotechnological applications over the last decade has raised an interest for the characterization of its mechanical properties and structure, and that includes approaches using Atomic Force Microscopy (AFM) and other single-molecule techniques. Recent reports have resolved the structure of dsDNA with AFM at unprecedented resolution. However, an equivalent study with dsRNA is still lacking. Here, we have visualized the double helix of dsRNA under near-physiological conditions and at sufficient resolution to resolve the A-form sub-helical pitch periodicity. We have employed different high-sensitive force-detection methods and obtained images with similar spatial resolution. Therefore, we show here that the limiting factors for high-resolution AFM imaging of soft materials in liquid medium are, rather than the imaging mode, the force between the tip and the sample and the sharpness of the tip apex.

Magnetic Force Microscopy in Liquids.

In this work, the use of magnetic force microscopy (MFM) to acquire images of magnetic nanostructures in liquid environments is presented. Optimization of the MFM signal acquisition in liquid media is performed and it is applied to characterize the magnetic signal of magnetite nanoparticles. The ability for detecting magnetic nanostructures along with the well-known capabilities of atomic force microscopy in liquids suggests potential applications in fields such as nanomedicine, nanobiotechnology, or nanocatalysis.