Site-Specific Integration of Hexagonal Boron Nitride Quantum Emitters on 2D DNA Origami Nanopores.

Optical emitters in hexagonal boron nitride (hBN) are promising probes for single-molecule sensing platforms. When engineered in nanoparticle form, they can be integrated as detectors in nanodevices, yet positional control at the nanoscale is lacking. Here we demonstrate the functionalization of DNA origami nanopores with optically active hBN nanoparticles (NPs) with nanometer precision. The NPs are active under three wavelengths of visible illumination and display both stable and blinking emission, enabling their accurate localization by using wide-field optical nanoscopy. Correlative opto-structural characterization reveals deterministic binding of bright, multicolor hBN NPs at the pore rim due to π-π stacking interactions at site-specific locations on the DNA origami. Our work provides a scalable, bottom-up approach toward deterministic assembly of solid-state emitters on arbitrary structural elements based on DNA origami. Such a nanoscale arrangement of optically active components can advance the development of single-molecule platforms, including optical nanopores and nanochannel sensors.

A Mechanically Tunable Quantum Dot in a Graphene Break Junction.

Graphene quantum dots (QDs) are intensively studied as platforms for the next generation of quantum electronic devices. Fine tuning of the transport properties in monolayer graphene QDs, in particular with respect to the independent modulation of the tunnel barrier transparencies, remains challenging and is typically addressed using electrostatic gating. We investigate charge transport in back-gated graphene mechanical break junctions and reveal Coulomb blockade physics characteristic of a single, high-quality QD when a nanogap is opened in a graphene constriction. By mechanically controlling the distance across the newly formed graphene nanogap, we achieve reversible tunability of the tunnel coupling to the drain electrode by 5 orders of magnitude, while keeping the source-QD tunnel coupling constant. The break junction device can therefore become a powerful platform to study the physical parameters that are crucial to the development of future graphene-based devices, including energy converters and quantum calorimeters.

Imaging of Optically Active Defects with Nanometer Resolution.

Point defects significantly influence the optical and electrical properties of solid-state materials due to their interactions with charge carriers, which reduce the band-to-band optical transition energy. There has been a demand for developing direct optical imaging methods that would allow in situ characterization of individual defects with nanometer resolution. Here, we demonstrate the localization and quantitative counting of individual optically active defects in monolayer hexagonal boron nitride using single molecule localization microscopy. By exploiting the blinking behavior of defect emitters to temporally isolate multiple emitters within one diffraction limited region, we could resolve two defect emitters with a point-to-point distance down to ten nanometers. The results and conclusion presented in this work add unprecedented dimensions toward future applications of defects in quantum information processing and biological imaging.

Geometrical Effect in 2D Nanopores.

A long-standing problem in the application of solid-state nanopores is the lack of the precise control over the geometry of artificially formed pores compared to the well-defined geometry in their biological counterpart, that is, protein nanopores. To date, experimentally investigated solid-state nanopores have been shown to adopt an approximately circular shape. In this Letter, we investigate the geometrical effect of the nanopore shape on ionic blockage induced by DNA translocation using triangular h-BN nanopores and approximately circular molybdenum disulfide (MoS2) nanopores. We observe a striking geometry-dependent ion scattering effect, which is further corroborated by a modified ionic blockage model. The well-acknowledged ionic blockage model is derived from uniform ion permeability through the 2D nanopore plane and hemisphere like access region in the nanopore vicinity. On the basis of our experimental results, we propose a modified ionic blockage model, which is highly related to the ionic profile caused by geometrical variations. Our findings shed light on the rational design of 2D nanopores and should be applicable to arbitrary nanopore shapes.

Controlling Catalyst Bulk Reservoir Effects for Monolayer Hexagonal Boron Nitride CVD.

Highly controlled Fe-catalyzed growth of monolayer hexagonal boron nitride (h-BN) films is demonstrated by the dissolution of nitrogen into the catalyst bulk via NH3 exposure prior to the actual growth step. This "pre-filling" of the catalyst bulk reservoir allows us to control and limit the uptake of B and N species during borazine exposure and thereby to control the incubation time and h-BN growth kinetics while also limiting the contribution of uncontrolled precipitation-driven h-BN growth during cooling. Using in situ X-ray diffraction and in situ X-ray photoelectron spectroscopy combined with systematic growth calibrations, we develop an understanding and framework for engineering the catalyst bulk reservoir to optimize the growth process, which is also relevant to other 2D materials and their heterostructures.

Nucleation control for large, single crystalline domains of monolayer hexagonal boron nitride via Si-doped Fe catalysts.

The scalable chemical vapor deposition of monolayer hexagonal boron nitride (h-BN) single crystals, with lateral dimensions of ∼0.3 mm, and of continuous h-BN monolayer films with large domain sizes (>25 µm) is demonstrated via an admixture of Si to Fe catalyst films. A simple thin-film Fe/SiO2/Si catalyst system is used to show that controlled Si diffusion into the Fe catalyst allows exclusive nucleation of monolayer h-BN with very low nucleation densities upon exposure to undiluted borazine. Our systematic in situ and ex situ characterization of this catalyst system establishes a basis for further rational catalyst design for compound 2D materials.

Long-Term Passivation of Strongly Interacting Metals with Single-Layer Graphene.

The long-term (>18 months) protection of Ni surfaces against oxidation under atmospheric conditions is demonstrated by coverage with single-layer graphene, formed by chemical vapor deposition. In situ, depth-resolved X-ray photoelectron spectroscopy of various graphene-coated transition metals reveals that a strong graphene-metal interaction is of key importance in achieving this long-term protection. This strong interaction prevents the rapid intercalation of oxidizing species at the graphene-metal interface and thus suppresses oxidation of the substrate surface. Furthermore, the ability of the substrate to locally form a passivating oxide close to defects or damaged regions in the graphene overlayer is critical in plugging these defects and preventing oxidation from proceeding through the bulk of the substrate. We thus provide a clear rationale for understanding the extent to which two-dimensional materials can protect different substrates and highlight the key implications for applications of these materials as barrier layers to prevent oxidation.

Interdependency of subsurface carbon distribution and graphene-catalyst interaction.

The dynamics of the graphene-catalyst interaction during chemical vapor deposition are investigated using in situ, time- and depth-resolved X-ray photoelectron spectroscopy, and complementary grand canonical Monte Carlo simulations coupled to a tight-binding model. We thereby reveal the interdependency of the distribution of carbon close to the catalyst surface and the strength of the graphene-catalyst interaction. The strong interaction of epitaxial graphene with Ni(111) causes a depletion of dissolved carbon close to the catalyst surface, which prevents additional layer formation leading to a self-limiting graphene growth behavior for low exposure pressures (10(-6)-10(-3) mbar). A further hydrocarbon pressure increase (to ∼10(-1) mbar) leads to weakening of the graphene-Ni(111) interaction accompanied by additional graphene layer formation, mediated by an increased concentration of near-surface dissolved carbon. We show that growth of more weakly adhered, rotated graphene on Ni(111) is linked to an initially higher level of near-surface carbon compared to the case of epitaxial graphene growth. The key implications of these results for graphene growth control and their relevance to carbon nanotube growth are highlighted in the context of existing literature.

Compliant DNA Origami Nanoactuators as Size-Selective Nanopores.

Biological nanopores crucially control the import and export of biomolecules across lipid membranes in cells. They have found widespread use in biophysics and biotechnology, where their typically narrow, fixed diameters enable selective transport of ions and small molecules, as well as DNA and peptides for sequencing applications. Yet, due to their small channel sizes, they preclude the passage of large macromolecules, e.g., therapeutics. Here, the unique combined properties of DNA origami nanotechnology, machine-inspired design, and synthetic biology are harnessed, to present a structurally reconfigurable DNA origami MechanoPore (MP) that features a lumen that is tuneable in size through molecular triggers. Controllable switching of MPs between 3 stable states is confirmed by 3D-DNA-PAINT super-resolution imaging and through dye-influx assays, after reconstitution of the large MPs in the membrane of liposomes via an inverted-emulsion cDICE technique. Confocal imaging of transmembrane transport shows size-selective behavior with adjustable thresholds. Importantly, the conformational changes are fully reversible, attesting to the robust mechanical switching that overcomes pressure from the surrounding lipid molecules. These MPs advance nanopore technology, offering functional nanostructures that can be tuned on-demand - thereby impacting fields as diverse as drug delivery, biomolecule sorting, and sensing, as well as bottom-up synthetic biology.

Low-cost acoustic force trap in a microfluidic channel.

A low-cost glass-based microfluidic flow cell with a piezo actuator is built using off-the-shelf parts (total cost €9 per device) to apply acoustophoretic force on polystyrene micro-beads. The main challenge in the fabrication of these devices was to ensure their leak tightness, which we solved using double-sided tape and nail polish. Beads with 1.5 µm diameter flowing in a 100 µm deep channel were trapped at 7.5 MHz using a 23.7 peak-to-peak voltage (Vpp) sinusoidal input. The trap located at 50 ± 0.1 µm depth was measured to have a stiffness of approximately 0.6 pN/µm. With this simple device we can trap and control the axial position of micrometer scale objects, which allows for the manipulation of beads and cells. We intend to use the device for force spectroscopy on micro-bead tethered DNA. This can be combined with super-resolution imaging techniques to study mechanics and binding of protein structures along a DNA strand as a function of induced tension.

Massively parallel fabrication of crack-defined gold break junctions featuring sub-3 nm gaps for molecular devices.

Break junctions provide tip-shaped contact electrodes that are fundamental components of nano and molecular electronics. However, the fabrication of break junctions remains notoriously time-consuming and difficult to parallelize. Here we demonstrate true parallel fabrication of gold break junctions featuring sub-3 nm gaps on the wafer-scale, by relying on a novel self-breaking mechanism based on controlled crack formation in notched bridge structures. We achieve fabrication densities as high as 7 million junctions per cm2, with fabrication yields of around 7% for obtaining crack-defined break junctions with sub-3 nm gaps of fixed gap width that exhibit electron tunneling. We also form molecular junctions using dithiol-terminated oligo(phenylene ethynylene) (OPE3) to demonstrate the feasibility of our approach for electrical probing of molecules down to liquid helium temperatures. Our technology opens a whole new range of experimental opportunities for nano and molecular electronics applications, by enabling very large-scale fabrication of solid-state break junctions.

Mechanically controlled quantum interference in graphene break junctions.

The ability to detect and distinguish quantum interference signatures is important for both fundamental research and for the realization of devices such as electron resonators1, interferometers2 and interference-based spin filters3. Consistent with the principles of subwavelength optics, the wave nature of electrons can give rise to various types of interference effects4, such as Fabry-Pérot resonances5, Fano resonances6 and the Aharonov-Bohm effect7. Quantum interference conductance oscillations8 have, indeed, been predicted for multiwall carbon nanotube shuttles and telescopes, and arise from atomic-scale displacements between the inner and outer tubes9,10. Previous theoretical work on graphene bilayers indicates that these systems may display similar interference features as a function of the relative position of the two sheets11,12. Experimental verification is, however, still lacking. Graphene nanoconstrictions represent an ideal model system to study quantum transport phenomena13-15 due to the electronic coherence16 and the transverse confinement of the carriers17. Here, we demonstrate the fabrication of bowtie-shaped nanoconstrictions with mechanically controlled break junctions made from a single layer of graphene. Their electrical conductance displays pronounced oscillations at room temperature, with amplitudes that modulate over an order of magnitude as a function of subnanometre displacements. Surprisingly, the oscillations exhibit a period larger than the graphene lattice constant. Charge-transport calculations show that the periodicity originates from a combination of the quantum interference and lattice commensuration effects of two graphene layers that slide across each other. Our results provide direct experimental observation of a Fabry-Pérot-like interference of electron waves that are partially reflected and/or transmitted at the edges of the graphene bilayer overlap region.

Insulator-to-Metallic Spin-Filtering in 2D-Magnetic Tunnel Junctions Based on Hexagonal Boron Nitride.

We report on the integration of atomically thin 2D insulating hexagonal boron nitride (h-BN) tunnel barriers into magnetic tunnel junctions (2D-MTJs) by fabricating two illustrative systems (Co/h-BN/Co and Co/h-BN/Fe) and by discussing h-BN potential for metallic spin filtering. The h-BN is directly grown by chemical vapor deposition on prepatterned Co and Fe stripes. Spin-transport measurements reveal tunnel magneto-resistances in these h-BN-based MTJs as high as 12% for Co/h-BN/h-BN/Co and 50% for Co/h-BN/Fe. We analyze the spin polarizations of h-BN/Co and h-BN/Fe interfaces extracted from experimental spin signals in light of spin filtering at hybrid chemisorbed/physisorbed h-BN, with support of ab initio calculations. These experiments illustrate the strong potential of h-BN for MTJs and are expected to ignite further investigations of 2D materials for large signal spin devices.

Introducing Overlapping Grain Boundaries in Chemical Vapor Deposited Hexagonal Boron Nitride Monolayer Films.

We demonstrate the growth of overlapping grain boundaries in continuous, polycrystalline hexagonal boron nitride (h-BN) monolayer films via scalable catalytic chemical vapor deposition. Unlike the commonly reported atomically stitched grain boundaries, these overlapping grain boundaries do not consist of defect lines within the monolayer films but are composed of self-sealing bilayer regions of limited width. We characterize this overlapping h-BN grain boundary structure in detail by complementary (scanning) transmission electron microscopy techniques and propose a catalytic growth mechanism linked to the subsurface/bulk of the process catalyst and its boron and nitrogen solubilities. Our data suggest that the overlapping grain boundaries are comparatively resilient against deleterious pinhole formation associated with grain boundary defect lines and thus may reduce detrimental breakdown effects when polycrystalline h-BN monolayer films are used as ultrathin dielectrics, barrier layers, or separation membranes.

Extrinsic Cation Selectivity of 2D Membranes.

From a systematic study of the concentration driven diffusion of positive and negative ions across porous 2D membranes of graphene and hexagonal boron nitride (h-BN), we prove their cation selectivity. Using the current-voltage characteristics of graphene and h-BN monolayers separating reservoirs of different salt concentrations, we calculate the reversal potential as a measure of selectivity. We tune the Debye screening length by exchanging the salt concentrations and demonstrate that negative surface charge gives rise to cation selectivity. Surprisingly, h-BN and graphene membranes show similar characteristics, strongly suggesting a common origin of selectivity in aqueous solvents. For the first time, we demonstrate that the cation flux can be increased by using ozone to create additional pores in graphene while maintaining excellent selectivity. We discuss opportunities to exploit our scalable method to use 2D membranes for applications including osmotic power conversion.

From Growth Surface to Device Interface: Preserving Metallic Fe under Monolayer Hexagonal Boron Nitride.

We investigate the interfacial chemistry between Fe catalyst foils and monolayer hexagonal boron nitride (h-BN) following chemical vapor deposition and during subsequent atmospheric exposure, using scanning electron microscopy, X-ray photoemission spectroscopy, and scanning photoelectron microscopy. We show that regions of the Fe surface covered by h-BN remain in a metallic state during exposure to moist air for ∼40 h at room temperature. This protection is attributed to the strong interfacial interaction between h-BN and Fe, which prevents the rapid intercalation of oxidizing species. Local Fe oxidation is observed on bare Fe regions and close to defects in the h-BN film (e.g., domain boundaries, wrinkles, and edges), which over the longer-term provide pathways for slow bulk oxidation of Fe. We further confirm that the interface between h-BN and metallic Fe can be recovered by vacuum annealing at ∼600 °C, although this is accompanied by the creation of defects within the h-BN film. We discuss the importance of these findings in the context of integrated manufacturing and transfer-free device integration of h-BN, particularly for technologically important applications where h-BN has potential as a tunnel barrier such as magnetic tunnel junctions.

Towards a general growth model for graphene CVD on transition metal catalysts.

The chemical vapour deposition (CVD) of graphene on three polycrystalline transition metal catalysts, Co, Ni and Cu, is systematically compared and a first-order growth model is proposed which can serve as a reference to optimize graphene growth on any elemental or alloy catalyst system. Simple thermodynamic considerations of carbon solubility are insufficient to capture even basic growth behaviour on these most commonly used catalyst materials, and it is shown that kinetic aspects such as carbon permeation have to be taken into account. Key CVD process parameters are discussed in this context and the results are anticipated to be highly useful for the design of future strategies for integrated graphene manufacture.

Efficient Transfer Doping of Carbon Nanotube Forests by MoO3.

We dope nanotube forests using evaporated MoO3 and observe the forest resistivity to decrease by 2 orders of magnitude, reaching values as low as ∼5 × 10(-5) Ωcm, thus approaching that of copper. Using in situ photoemission spectroscopy, we determine the minimum necessary MoO3 thickness to dope a forest and study the underlying doping mechanism. Homogenous coating and tube compaction emerge as key factors for decreasing the forest resistivity. When all nanotubes are fully coated with MoO3 and packed, conduction channels are created both inside the nanotubes and on the outside oxide layer. This is supported by density functional theory calculations, which show a shift of the Fermi energy of the nanotubes and the conversion of the oxide into a layer of metallic character. MoO3 doping removes the need for chirality control during nanotube growth and represents a step forward toward the use of forests in next-generation electronics and in power cables or conductive polymers.

Co-catalytic absorption layers for controlled laser-induced chemical vapor deposition of carbon nanotubes.

The concept of co-catalytic layer structures for controlled laser-induced chemical vapor deposition of carbon nanotubes is established, in which a thin Ta support layer chemically aids the initial Fe catalyst reduction. This enables a significant reduction in laser power, preventing detrimental positive optical feedback and allowing improved growth control. Systematic study of experimental parameters combined with simple thermostatic modeling establishes general guidelines for the effective design of such catalyst/absorption layer combinations. Local growth of vertically aligned carbon nanotube forests directly on flexible polyimide substrates is demonstrated, opening up new routes for nanodevice design and fabrication.