Selective Growth of van der Waals Heterostructures Enabled by Electron-Beam Irradiation.

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.

High durability and stability of 2D nanofluidic devices for long-term single-molecule sensing.

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 MoS2, 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 MoS2 nanopores. We identify chemical oxidation and delamination of monolayers from their underlying substrates as the major reasons for the instability of MoS2 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.

Wafer-scale MoS2 with water-vapor assisted showerhead MOCVD.

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.

High-Throughput Nanopore Fabrication and Classification Using Xe-Ion Irradiation and Automated Pore-Edge Analysis.

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.

Stress induced delamination of suspended MoS2 in aqueous environments.

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.

Engineering Optically Active Defects in Hexagonal Boron Nitride Using Focused Ion Beam and Water.

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.

Superconducting 2D NbS2 Grown Epitaxially by Chemical Vapor Deposition.

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.

Super-resolved Optical Mapping of Reactive Sulfur-Vacancies in Two-Dimensional Transition Metal Dichalcogenides.

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.

Wetting of nanopores probed with pressure.

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.

Pressure-Induced Enlargement and Ionic Current Rectification in Symmetric Nanopores.

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.