Fabrication of Atomically Precise Nanopores in Hexagonal Boron Nitride

We demonstrate the fabrication of individual nanopores in hexagonal boron nitride (hBN) with atomically precise control of the pore size. Previous methods of pore production in other 2D materials create pores of irregular geometry with imprecise diameters. By taking advantage of the preferential growth of boron vacancies in hBN under electron beam irradiation, we are able to observe the pore growth via transmission electron microscopy, and terminate the process when the pore has reached its desired size. Careful control of beam conditions allows us to nucleate and grow individual triangular and hexagonal pores with diameters ranging from subnanometer to 6nm over a large area of suspended hBN using a conventional TEM. These nanopores could find application in molecular sensing, DNA sequencing, water desalination, and molecular separation. Furthermore, the chemical edge-groups along the hBN pores can be made entirely nitrogen terminated or faceted with boron-terminated edges, opening avenues for tailored functionalization and extending the applications of these hBN nanopores.Comment: 5 pages, 6 figure

Characterizing Transition-Metal Dichalcogenide Thin-Films using Hyperspectral Imaging and Machine Learning

Atomically thin polycrystalline transition-metal dichalcogenides (TMDs) are relevant to both fundamental science investigation and applications. TMD thin-films present uniquely difficult challenges to effective nanoscale crystalline characterization. Here we present a method to quickly characterize the nanocrystalline grain structure and texture of monolayer WS2 films using scanning nanobeam electron diffraction coupled with multivariate statistical analysis of the resulting data. Our analysis pipeline is highly generalizable and is a useful alternative to the time consuming, complex, and system-dependent methodology traditionally used to analyze spatially resolved electron diffraction measurements

Alternative Stacking Sequences in Hexagonal Boron Nitride

The relative orientation of successive sheets, i.e. the stacking sequence, in layered two-dimensional materials is central to the electronic, thermal, and mechanical properties of the material. Often different stacking sequences have comparable cohesive energy, leading to alternative stable crystal structures. Here we theoretically and experimentally explore different stacking sequences in the van der Waals bonded material hexagonal boron nitride (h-BN). We examine the total energy, electronic bandgap, and dielectric response tensor for five distinct high symmetry stacking sequences for both bulk and bilayer forms of h-BN. Two sequences, the generally assumed AA' sequence and the relatively unknown (for h-BN) AB (Bernal) sequence, are predicted to have comparably low energy. We present a scalable modified chemical vapor deposition method that produces large flakes of virtually pure AB stacked h-BN; this new material complements the generally available AA' stacked h-BN

Blue-Light-Emitting Color Centers in High-Quality Hexagonal Boron Nitride

Light emitters in wide band gap semiconductors are of great fundamental interest and have potential as optically addressable qubits. Here we describe the discovery of a new color center in high-quality hexagonal boron nitride (h-BN) with a sharp emission line at 435 nm. The emitters are activated and deactivated by electron beam irradiation and have spectral and temporal characteristics consistent with atomic color centers weakly coupled to lattice vibrations. The emitters are conspicuously absent from commercially available h-BN and are only present in ultra-high-quality h-BN grown using a high-pressure, high-temperature Ba-B-N flux/solvent, suggesting that these emitters originate from impurities or related defects specific to this unique synthetic route. Our results imply that the light emission is activated and deactivated by electron beam manipulation of the charge state of an impurity-defect complex

Dark-field transmission electron microscopy and the Debye-Waller factor of graphene

Graphene\u27s structure bears on both the material\u27s electronic properties and fundamental questions about long-range order in two-dimensional crystals. We present an analytic calculation of selected area electron diffraction from multilayer graphene and compare it with data from samples prepared by chemical vapor deposition and mechanical exfoliation. A single layer scatters only 0.5% of the incident electrons, so this kinematical calculation can be considered reliable for five or fewer layers. Dark-field transmission electron micrographs of multilayer graphene illustrate how knowledge of the diffraction peak intensities can be applied for rapid mapping of thickness, stacking, and grain boundaries. The diffraction peak intensities also depend on the mean-square displacement of atoms from their ideal lattice locations, which is parameterized by a Debye-Waller factor. We measure the Debye-Waller factor of a suspended monolayer of exfoliated graphene and find a result consistent with an estimate based on the Debye model. For laboratory-scale graphene samples, finite size effects are sufficient to stabilize the graphene lattice against melting, indicating that ripples in the third dimension are not necessary

Tunable Electronic Structure in Gallium Chalcogenide van der Waals Compounds

Transition metal monochalcogenides comprise a class of two-dimensional materials with electronic band gaps that are highly sensitive to material thickness and chemical composition. Here, we explore the tunability of the electronic excitation spectrum in GaSe using angle-resolved photoemission spectroscopy. The electronic structure of the material is modified by $\textit{in-situ}$ potassium deposition as well as by forming GaS$_{x}$Se$_{1-x}$ alloy compounds. We find that potassium decouples the top-most tetra-layer of the GaSe unit cell, leading to a substantial change of the dispersion around the valence band maximum (VBM). The observed band dispersion of a single tetralayer is consistent with a transition from the direct gap character of the bulk to the indirect gap character expected for monolayer GaSe. Upon alloying with sulfur, we observe a phase transition from AB to $\text{AA}^{\prime}$ stacking. Alloying also results in a rigid energy shift of the VBM towards higher binding energies which correlates with a blue shift in the luminescence. The increase of the band gap upon sulfur alloying does not appear to change the dispersion or character of the VBM appreciably, implying that it is possible to engineer the gap of these materials while maintaining their salient electronic properties

Dark-field transmission electron microscopy and the Debye-Waller factor of graphene

Graphene's structure bears on both the material's electronic properties and fundamental questions about long range order in two-dimensional crystals. We present an analytic calculation of selected area electron diffraction from multi-layer graphene and compare it with data from samples prepared by chemical vapor deposition and mechanical exfoliation. A single layer scatters only 0.5% of the incident electrons, so this kinematical calculation can be considered reliable for five or fewer layers. Dark-field transmission electron micrographs of multi-layer graphene illustrate how knowledge of the diffraction peak intensities can be applied for rapid mapping of thickness, stacking, and grain boundaries. The diffraction peak intensities also depend on the mean-square displacement of atoms from their ideal lattice locations, which is parameterized by a Debye-Waller factor. We measure the Debye-Waller factor of a suspended monolayer of exfoliated graphene and find a result consistent with an estimate based on the Debye model. For laboratory-scale graphene samples, finite size effects are sufficient to stabilize the graphene lattice against melting, indicating that ripples in the third dimension are not necessary.Comment: 10 pages, 4 figure