Interferometric scattering microscopy (iSCAT) is a label-free imaging technique that achieves single-molecule spatial and milli-second temporal resolution. In this technique, we use the combination of reflected and scattered light of the nanoparticle itself as our signal obviating the need of a label or tags as commonly used in fluorescence microscopy. With iSCAT, photobleaching is not an issue as the signal donor (the particle of interest) provides an infinite budget of scattered photons and hence indefinite imaging times.

Van der Waals heterostructures (vdWHSs) enable the fabrication of complex electronic devices based on two-dimensional (2D) materials. Ideally, these vdWHSs should be fabricated in a scalable and repeatable way and only in the specific areas of the substrate to lower the number of technological operations inducing defects and impurities. Here, we present a method of selective fabrication of vdWHSs via chemical vapor deposition by electron-beam (EB) irradiation. We distinguish two growth modes: positive (2D materials nucleate on the irradiated regions) on graphene and tungsten disulfide (WS2) substrates, and negative (2D materials do not nucleate on the irradiated regions) on the graphene substrate. The growth mode is controlled by limiting the air exposure of the irradiated substrate and the time between irradiation and growth. We conducted Raman mapping, Kelvin-probe force microscopy, X-ray photoelectron spectroscopy, and density-functional theory modeling studies to investigate the selective growth mechanism. We conclude that the selective growth is explained by the competition of three effects: EB-induced defects, adsorption of carbon species, and electrostatic interaction. The method here is a critical step toward the industry-scale fabrication of 2D-materials-based devices.

2D materials offer huge potential as substrates to build devices for biosensing applications but are plagued by unwanted interactions such as binding/sticking. Controlling such interactions will be critical for the continued exploration of 2D materials in biosensing. In this work, we engineer and tune the surface interactions of hexagonal boron nitride (hBN) to direct the motion and diffusion of DNA. Using ISCAT and fluorescence microscopy techniques, we explore the nanoscopic interactions of DNA with different 2D materials. We show that pristine hBN flakes exhibit the lowest surface interactions and DNA bind preferentially to the edges and regions of high defect density of the hBN flake. We tap into a recently reported Xenon Focused Ion Beam (FIB) technique to engineer edges and defects on hBN flakes. Our technique harnesses a Xenon-FIB to lightly irradiate the desired regions of the hBN flake followed by subsequent etching in water which allows for a much cleaner hBN surface. We are able to enhance DNA binding and affinity at defined locations by inducing defects using FIB. By creating long tracks of defects, we induce diffusion along our created tracks, thereby allowing us to direct motion of the DNA molecules. We envision future devices where such engineered interactions are able to direct biomolecules to sensing regions (such as a nanopore) on 2D material based devices thereby increasing the rate of analyte capture and sensitivity of single molecule sensing devices.

Nanopores in two-dimensional (2D) membranes hold immense potential in single-molecule sensing, osmotic power generation, and information storage. Recent advances in 2D nanopores, especially on single-layer MoS 2 , focus on the scalable growth and manufacturing of nanopore devices. However, there still remains a bottleneck in controlling the nanopore stability in atomically thin membranes. Here, we evaluate the major factors responsible for the instability of the monolayer MoS 2 nanopores. We identify chemical oxidation and delamination of monolayers from their underlying substrates as the major reasons for the instability of MoS 2 nanopores. Surface modification of the substrate and reducing the oxygen from the measurement solution improves nanopore stability and dramatically increases their shelf-life. Understanding nanopore growth and stability can provide insights into controlling the pore size, shape and can enable long-term measurements with a high signal-to-noise ratio and engineering durable nanopore devices.

Applying hydrostatic pressure with suspended 2D material thin membranes allows probing the effects of lateral strain on the ion and fluid transport through nanopores. We demonstrate how both permanent and temporary delamination of 2D materials can be induced by pressure and potential differences between the membrane, causing a strong mechanosensitive modulation of ion transport. Our methodology is based on in situ measurements of ionic current and streaming modulation as the supporting membrane is indented or bulged with pressure. We demonstrate how indirect measurements of fluid transport through delaminated MoS2 membranes is achieved through monitoring streaming current and potential. This is combined with TEM images of 2D material membranes before and after aqueous measurements, showing temporary delamination during mechanical or electrical stress. The obtained results allow a better understanding of measurements with supported 2D materials, i.e. avoiding misinterpreting measured data, and could be used to probe how the electrical field and fluid flow at the nanoscale influence the adhesion of supported 2D materials.

Large-area nanopore drilling is a major bottleneck in state-of-the-art nanoporous 2D membrane fabrication protocols. In addition, high-quality structural and statistical descriptions of as-fabricated porous membranes are key to predicting the corresponding membrane-wide permeation properties. In this work, we investigate Xe-ion focused ion beam as a tool for scalable, large-area nanopore fabrication on atomically thin, free-standing molybdenum disulfide. The presented irradiation protocol enables designing ultrathin membranes with tunable porosity and pore dimensions, along with spatial uniformity across large-area substrates. Fabricated nanoporous membranes are then characterized using scanning transmission electron microscopy imaging, and the observed nanopore geometries are analyzed through a pore-edge detection and analysis script. We further demonstrate that the obtained structural and statistical data can be readily passed on to computational and analytical tools to predict the permeation properties at both individual pore and membrane-wide scales. As an example, membranes featuring angstrom-scale pores are investigated in terms of their emerging water and ion flow properties through extensive all-atom molecular dynamics simulations. We believe that the combination of experimental and analytical approaches presented here will yield accurate physics-based property estimates and thus potentially enable a true function-by-design approach to fabrication for applications such as osmotic power generation and desalination/filtration.

Van der Waals heterostructures (vdWHSs) provide a unique playground to study fundamental physics and practical applications of two-dimensional (2D) materials. However, most 2D heterostructures are prepared by transfer, hindering their technological implementation. Here, we report the first chemical vapour deposition of monolayered MoS2/WS2/graphene vertical vdWHS without transfer step. By atomic force microscopy, photoluminescence, Raman spectroscopy, and secondary ion mass spectroscopy, we confirmed the vertical stacking of three different 2D materials. The use of WS2, graphene, and sapphire as growth substrates allowed us to describe the 2D materials growth process better. We determined that for the synthesis of 2D materials, only the chemical potential of the crystal formation and the substrate-layer adhesion energy are relevant factors. In addition, we used MoS2/WS2/graphene vdWHS to fabricate a photoresponsive memory device, showing the application potential of such heterostacks. Our results clarify the growth mechanisms of 2D materials and pave the way for the growth of more complex vdWHSs.

Hexagonal boron nitride (hBN) has emerged as a promising material platform for nanophotonics and quantum sensing, hosting optically active defects with exceptional properties such as high brightness and large spectral tuning. However, precise control over deterministic spatial positioning of emitters in hBN remained elusive for a long time, limiting their proper correlative characterization and applications in hybrid devices. Recently, focused ion beam (FIB) systems proved to be useful to engineer several types of spatially defined emitters with various structural and photophysical properties. Here we systematically explore the physical processes leading to the creation of optically active defects in hBN using FIB and find that beam-substrate interaction plays a key role in the formation of defects. These findings are confirmed using transmission electron microscopy, which reveals local mechanical deterioration of the hBN layers and local amorphization of ion beam irradiated hBN. Additionally, we show that, upon exposure to water, amorphized hBN undergoes a structural and optical transition between two defect types with distinctive emission properties. Moreover, using super-resolution optical microscopy combined with atomic force microscopy, we pinpoint the exact location of emitters within the defect sites, confirming the role of defected edges as primary sources of fluorescent emission. This lays the foundation for FIB-assisted engineering of optically active defects in hBN with high spatial and spectral control for applications ranging from integrated photonics, to nanoscale sensing, and to nanofluidics.

Among numerous thin film synthesis methods, metalorganic chemical vapor deposition performed in a showerhead reactor is the most promising one for broad use in scalable and commercially adaptable two-dimensional material synthesis processes. Adapting the most efficient monolayer growth methodologies from tube-furnace systems to vertical-showerhead geometries allows us to overcome the intrinsic process limitations and improve the overall monolayer yield quality. Here, we demonstrate large-area, monolayer molybdenum disulphide growth by combining gas-phase precursor supply with unique tube-furnace approaches of utilizing sodium molybdate pre-seeding solution spincoated on a substrate along with water vapor added during the growth step. The engineered process yields a high-quality, 4-inch scale monolayer film on sapphire wafers. The monolayer growth coverage, average crystal size and defect density were evaluated using Raman and photoluminescence spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy and scanning transmission electron microscopy imaging. Our findings provide a direct step forward toward developing a reproducible and large-scale MoS2 synthesis with commercial showerhead reactors.

Nanopores are both a tool to study single-molecule biophysics and nanoscale ion transport, but also a promising material for desalination or osmotic power generation. Understanding the physics underlying ion transport through nano-sized pores allows better design of porous membrane materials. Material surfaces can present hydrophobicity, a property which can make them prone to formation of surface nanobubbles. Nanobubbles can influence the electrical transport properties of such devices. We demonstrate an approach which uses hydraulic pressure to probe the electrical transport properties of solid state nanopores. We show how pressure can be used to wet pores, and how it allows control over bubbles or other contaminants in the nanometer scale range normally unachievable using only an electrical driving force. Molybdenum disulfide is then used as a typical example of a 2D material on which we demonstrate wetting and bubble induced nonlinear and linear conductance in the regimes typically used with these experiments. We show that by using pressure one can identify and evade wetting artifacts.

Tailoring the surface properties of 2D materials, such as transition metal dichalcogenides (TMDCs), at the nanoscale is becoming essential in the fabrication of various 2D material-based nanoelectronic devices. Due to the chemical inertness of their basal plane, the surface modification of 2D TMDCs is limited to their defective sites, often requiring special treatments, such as the conversion of the TMDC from its semiconducting into its metallic phase. In this work, we show that the basal plane of a semiconducting 2D TMDC, molybdenum disulfide (MoS2) can be modified electrochemically by electrografting of aryl-diazonium salt. To demonstrate the advantages of this method at the nanoscale, we perform electrografting of 3,5-bis(trifluoromethyl)benzenediazonium tetrafluoroborate on predefined MoS2 nanoribbons by addressing them individually via a different electrode. The ability to selectively address individually contacted 2D layers opens the possibility for specific surface modification of neighboring 2D nanostructures by different functional groups. This method could be extended to other aryl-diazonium compounds, and other 2D semiconducting materials.

Transition metal dichalcogenides (TMDs) represent a class of semiconducting two-dimensional (2D) materials with exciting properties. In particular, defects in 2D-TMDs and their molecular interactions with the environment can crucially affect their physical and chemical properties. However, mapping the spatial distribution and chemical reactivity of defects in liquid remains a challenge. Here, we demonstrate large area mapping of reactive sulfur-deficient defects in 2D-TMDs in aqueous solutions by coupling single-molecule localization microscopy with fluorescence labeling using thiol chemistry. Our method, reminiscent of PAINT strategies, relies on the specific binding of fluorescent probes hosting a thiol group to sulfur vacancies, allowing localization of the defects with an uncertainty down to 15 nm. Tuning the distance between the fluorophore and the docking thiol site allows us to control Föster resonance energy transfer (FRET) process and reveal grain boundaries and line defects due to the local irregular lattice structure. We further characterize the binding kinetics over a large range of pH conditions, evidencing the reversible adsorption of the thiol probes to the defects with a subsequent transitioning to irreversible binding in basic conditions. Our methodology provides a simple and fast alternative for large-scale mapping of nonradiative defects in 2D materials and can be used for in situ and spatially resolved monitoring of the interaction between chemical agents and defects in 2D materials that has general implications for defect engineering in aqueous condition.

Metallic two-dimensional (2D) transition metal dichalcogenides (TMDCs) are attracting great attention because of their interesting low-temperature properties such as superconductivity, magnetism, and charge density waves (CDW). However, further studies and practical applications are being slowed down by difficulties in synthesizing high-quality materials with a large grain size and well-determined thickness. In this work, we demonstrate epitaxial chemical vapor deposition (CVD) growth of 2D NbS2 crystals on a sapphire substrate, with a thickness-dependent structural phase transition. NbS2 crystals are epitaxially aligned by the underlying c-plane sapphire resulting in high-quality growth. The thickness of NbS2 is well controlled by growth parameters to be between 1.5 and 10 nm with a large grain size of up to 500 μm. As the thickness increases, we observe in our NbS2 a transition from a metallic 3R-polytype to a superconducting 2H-polytype, confirmed by Raman spectroscopy, aberration-corrected scanning transmission electron microscopy (STEM) and electrical transport measurements. A Berezinskii-Kosterlitz-Thouless (BKT) superconducting transition occurs in the CVD-grown 2H-phase NbS2 below the transition temperature (Tc) of 3 K. Our work demonstrates thickness and phase-controllable synthesis of high-quality superconducting 2D NbS2, which is imperative for its practical applications in next-generation TMDC-based electrical devices.

Nanopores in solid state membranes are a tool able to probe nanofluidic phenomena or can act as a single molecular sensor. They also have diverse applications in filtration, desalination, or osmotic power generation. Many of these applications involve chemical, or hydrostatic pressure differences which act on both the supporting membrane, and the ion transport through the pore. By using pressure differences between the sides of the membrane and an alternating current approach to probe ion transport, we investigate two distinct physical phenomena: the elastic deformation of the membrane through the measurement of strain at the nanopore, and the growth of ionic current rectification with pressure due to pore entrance effects. These measurements are a significant step toward the understanding of the role of elastic membrane deformation or fluid flow on linear and nonlinear transport properties of nanopores.

Atomically thin (2D) nanoporous membranes are an excellent platform for a broad scope of academic research. Their thickness and intrinsic ion selectivity (demonstrated for example in molybdenum disulfide-MoS2) make them particularly attractive for single-molecule biosensing experiments and osmotic energy harvesting membranes. Currently, one of the major challenges associated with the research progress and industrial development of 2D nanopore membrane devices is small-scale thin-film growth and small-area transfer methods. To address these issues, a large-area protocol including a wafer-scale monolayer MoS2 synthesis, Si/SiNx substrate fabrication and wafer-scale material transfer are demonstrated. First, the 7.62 cm wafer-scale MOCVD growth yielding homogenous monolayer MoS2 films are introduced. Second, a large number of devices are fabricated in one batch by employing the wafer-scale thin-film transfer method with high transfer efficiency (>70% device yield). The growth, the transfer quality and cleanliness are investigated using transmission electron microscopy, atomic force microscopy and Raman spectroscopy. Finally, the applicability and robustness of the large-area protocol is demonstrated by performing a set of double-stranded DNA translocation experiments through as-fabricated MoS2 nanopore devices. It is believed that the shown approach will pave the way toward wafer-scale, high-throughput use of 2D nanopores in various applications.

Transition metal dichalcogenides (TMDs) represent an entire new class of semiconducting 2D materials with exciting properties. Defects in 2D TMDs can crucially affect their physical and chemical properties. However, characterization of the presence and spatial distribution of defects is limited either in throughput or in resolution. Here, we demonstrate large area mapping of reactive sulfur-deficient defects in 2D-TMDs coupling single-molecule localization microscopy with fluorescence labeling using thiol chemistry. Our method, reminiscent of PAINT strategies, relies on the specific binding by reversible physisorption of fluorescent probes to sulfur-vacancies via a thiol group and their intermittent emission to apply localization of the labeled defects with a precision down to 15 nm. Tuning the distance between the fluorophore and the docking thiol site allows us to control Föster Resonance Energy Transfer (FRET) process and reveal large structural defects such as grain boundaries and line defects, due to the local irregular lattice structure. Our methodology provides a simple and fast alternative for large-scale mapping of non-radiative defects in 2D materials and paves the way for in-situ and spatially resolved monitoring of the interaction between chemical agent and the defects in 2D materials that has general implications for defect engineering in aqueous condition.

Nanopores are both a tool to study single-molecule biophysics and nanoscale ion transport, but also a promising material for desalination or osmotic power generation. Understanding the physics underlying ion transport through nano-sized pores allows better design of porous membrane materials. Material surfaces can present hydrophobicity, a property which can make them prone to formation of surface nanobubbles. Nanobubbles can influence the electrical transport properties of such devices. We demonstrate an approach which uses hydraulic pressure to probe the electrical transport properties of solid state nanopores. We demonstrate how pressure can be used to wet pores, and how it allows control over bubbles in the nanometer scale range normally unachievable using only an electrical driving force. Molybdenum disulfide is then used as a typical example of a 2D material on which we demonstrate wetting and bubble induced nonlinear and linear conductance in the regimes typically used with these experiments. We show that by using pressure one can identify and evade wetting artifacts due to nanobubbles.

High-quality and large-scale growth of monolayer molybdenum disulfide (MoS2) has caught intensive attention because of its potential in many applications due to unique electronic properties. Here, we report the wafer-scale growth of high-quality monolayer MoS2 on singlecrystalline sapphire and also on SiO2 substrates by a facile metal-organic chemical vapor deposition (MOCVD) method. Prior to growth, an aqueous solution of sodium molybdate (Na2MoO4) is spun onto the substrates as the molybdenum precursor and diethyl sulfide ((C2H5)2S) is used as the sulfur precursor during the growth. The grown MoS2 films exhibit crystallinity, good electrical performance (electron mobility of 22 cm2·V-1·s-1) and structural continuity maintained over the entire wafer. The sapphire substrates are reusable for subsequent growth. The same method is applied for the synthesis of tungsten disulfide (WS2). Our work provides a facile, reproducible and cost-efficient method for the scalable fabrication of high-quality monolayer MoS2 for versatile applications, such as electronic and optoelectronic devices as well as the membranes for desalination and power generation.

Osmotic power generation, the extraction of power from mixing salt solutions of different concentrations, can provide an efficient power source for both nanoscale and industrial-level applications. Power is generated using ion-selective channels or pores of nanometric dimensions in synthetic membrane materials. 2D materials such as graphene and MoS 2 provide energy extraction efficiencies that are several orders of magnitude higher than those of more established bulky membranes. In this Review, we survey the current state of the art in power generation with both 2D materials and solid-state devices. We discuss the current understanding of the processes underlying power generation in boron nitride nanotubes and 2D materials, as well as the available fabrication methods and their impact on power generation. Finally, we overview future directions of research, which include increasing efficiency, upscaling single pores to porous membranes and solving other issues related to the potential practical application of 2D materials for osmotic power generation.