Inert Liquid Exfoliation and Langmuir-Type Thin Film Deposition of Semimetallic Metal Diborides.

Graphite is one of only a few layered materials that can be exfoliated into nanosheets with semimetallic properties, which limits the applications of nanosheet-based electrodes to material combinations compatible with the work function of graphene. It is therefore important to identify additional metallic or semimetallic two-dimensional (2D) nanomaterials that can be processed in solution for scalable fabrication of printed electronic devices. Metal diborides represent a family of layered non-van der Waals crystals with semimetallic properties for all nanosheet thicknesses. While previous reports show that the exfoliated nanomaterial is prone to oxidation, we demonstrate a readily accessible inert exfoliation process to produce quasi-2D nanoplatelets with intrinsic material properties. For this purpose, we demonstrate the exfoliation of three representative metal diborides (MgB2, CrB2, and ZrB2) under inert conditions. Nanomaterial is characterized using a combination of transmission electron microscopy, scanning electron microscopy, atomic force microscopy, IR, and UV-vis measurements, with only minimal oxidation indicated postprocessing. By depositing the pristine metal diboride nanoplatelets as thin films using a Langmuir-type deposition technique, the ohmic behavior of the networks is validated. Furthermore, the material decomposition is studied by using a combination of electrical and optical measurements after controlled exposure to ambient conditions. Finally, we report an efficient, low-cost approach for sample encapsulation to protect the nanomaterials from oxidation. This is used to demonstrate low-gauge factor strain sensors, confirming metal diboride nanosheets as a suitable alternative to graphene for electrode materials in printed electronics.

Heterocontact-Triggered 1H to 1T' Phase Transition in CVD-Grown Monolayer MoTe2: Implications for Low Contact Resistance Electronic Devices.

Single-layer molybdenum ditelluride (MoTe2) has attracted attention due to the smaller energy difference between the semiconducting (1H) and semimetallic (1T') phases with respect to other two-dimensional transition metal dichalcogenides (TMDs). Understanding the phenomenon of polymorphism between these structural phases is of great fundamental and practical importance. In this paper, we report a 1H to 1T' phase transition occurring during the chemical vapor deposition (CVD) synthesis of single-layer MoTe2 at 730 °C. The transformation originates at the heterocontact between monoclinic and hexagonal crystals and progresses to either yield a partial or complete 1H to 1T' phase transition. Microscopic and spectroscopic analyses of the MoTe2 crystals reveal the presence of Te vacancies and mirror twin boundaries (MTB) domains in the hexagonal phase. The experimental observations and theoretical simulations indicate that the combination of heterocontact formation and Te vacancies are relevant triggering mechanisms in the observed transformation. By advancing in the understanding and controlling of the direct synthesis of lateral 1T'/1H heterostructures, this work contributes to the development of MoTe2-based electronic and optoelectronic devices with low contact resistance.

Evaluation of TEM methods for their signature of the number of layers in mono- and few-layer TMDs as exemplified by MoS2 and MoTe2.

In mono- and few-layer 2D materials, the exact number of layers is a critical parameter, determining the materials' properties and thus their performance in future nano-devices. Here, we evaluate in a systematic manner the signature of exfoliated free-standing mono- and few-layer MoS2 and MoTe2 in TEM experiments such as high-resolution transmission electron microscopy, electron energy-loss spectroscopy, and 3D electron diffraction. A reference for the number of layers has been determined by optical contrast and AFM measurements on a substrate. Comparing the results, we discuss strengths and limitations, benchmarking the three TEM methods with respect to their ability to identify the exact number of layers.

Lattice contrast in the core-loss EFTEM signal of graphene.

The realization of chromatic aberration correction enables energy-filtered transmission electron microscopy (EFTEM) at atomic resolution even for large energy windows. Previous works have demonstrated lattice contrast from ionization-edge signals such as the L2,3 edges of silicon or titanium. However, the direct interpretation as chemical information was found to be hampered by contributions from elastic contrast with dynamic scattering, especially for thick samples. Here we demonstrate that even for thin samples with light atoms, the interpretation of the ionization-edge signal is complicated by inversions from bright-atom to dark-atom contrast. Our EFTEM experiments for graphene show lattice contrast in the carbon K-edge signal, and we find bright-atom and dark-atom contrast for different defoci.

Proton and Li-Ion Permeation through Graphene with Eight-Atom-Ring Defects.

Defect-free graphene is impermeable to gases and liquids but highly permeable to thermal protons. Atomic-scale defects such as vacancies, grain boundaries, and Stone-Wales defects are predicted to enhance graphene's proton permeability and may even allow small ions through, whereas larger species such as gas molecules should remain blocked. These expectations have so far remained untested in experiment. Here, we show that atomically thin carbon films with a high density of atomic-scale defects continue blocking all molecular transport, but their proton permeability becomes ∼1000 times higher than that of defect-free graphene. Lithium ions can also permeate through such disordered graphene. The enhanced proton and ion permeability is attributed to a high density of eight-carbon-atom rings. The latter pose approximately twice lower energy barriers for incoming protons compared to that of the six-atom rings of graphene and a relatively low barrier of ∼0.6 eV for Li ions. Our findings suggest that disordered graphene could be of interest as membranes and protective barriers in various Li-ion and hydrogen technologies.

Selective ion sieving through arrays of sub-nanometer nanopores in chemically tunable 2D carbon membranes.

Two-dimensional (2D) membranes featuring arrays of sub-nanometer pores have applications in purification, solvent separation and water desalination. Compared to channels in bulk membranes, 2D nanopores have lower resistance to transmembrane transport, leading to faster passage of ions. However, the formation of nanopores in 2D membranes requires expensive post-treatment using plasma or ion bombardment. Here, we study bottom-up synthesized porous carbon nanomembranes (CNMs) of biphenyl thiol (BPT) precursors. Sub-nanometer pores arise intrinsically during the BPT-CNM synthesis with a density of 2 ± 1 pore per 100 nm2. We employ BPT-CNM based pore arrays as efficient ion sieving channels, and demonstrate selectivity of the membrane towards ion transport when exposed to a range of concentration gradients of KCl, CsCl and MgCl2. The selectivity of the membrane towards K+ over Cl- ions is found be 16.6 mV at a 10 : 1 concentration ratio, which amounts to ∼30% efficiency relative to the Nernst potential for complete ion rejection. The pore arrays in the BPT-CNM show similar transport and selectivity properties to graphene and carbon nanotubes, whilst the fabrication method via self-assembly offers a facile means to control the chemical and physical properties of the membrane, such as surface charge, chemical nature and pore density. CNMs synthesized from self-assembled monolayers open the way towards the rational design of 2D membranes for selective ion sieving.

Bottom-Up Synthesis of Graphene Monolayers with Tunable Crystallinity and Porosity.

We present a method for a bottom-up synthesis of atomically thin graphene sheets with tunable crystallinity and porosity using aromatic self-assembled monolayers (SAMs) as molecular precursors. To this end, we employ SAMs with pyridine and pyrrole constituents on polycrystalline copper foils and convert them initially into molecular nanosheets-carbon nanomembranes (CNMs)- via low-energy electron irradiation induced cross-linking and then into graphene monolayers via pyrolysis. As the nitrogen atoms are leaving the nanosheets during pyrolysis, nanopores are generated in the formed single-layer graphene. We elucidate the structural changes upon the cross-linking and pyrolysis down to the atomic scale by complementary spectroscopy and microscopy techniques including X-ray photoelectron and Raman spectroscopy, low energy electron diffraction, atomic force, helium ion, and high-resolution transmission electron microscopy, and electrical transport measurements. We demonstrate that the crystallinity and porosity of the formed graphene can be adjusted via the choice of molecular precursors and pyrolysis temperature, and we present a kinetic growth model quantitatively describing the conversion of molecular CNMs into graphene. The synthesized nanoporous graphene monolayers resemble a percolated network of graphene nanoribbons with a high charge carrier mobility (∼600 cm2/(V s)), making them attractive for implementations in electronic field-effect devices.

Atomic scale microstructure and properties of Se-deficient two-dimensional MoSe2.

We study the atomic scale microstructure of nonstoichiometric two-dimensional (2D) transition metal dichalcogenide MoSe2-x by employing aberration-corrected high-resolution transmission electron microscopy. We show that a Se-deficit in single layers of MoSe2 grown by molecular beam epitaxy gives rise to a dense network of mirror-twin-boundaries (MTBs) decorating the 2D-grains. With the use of density functional theory calculations, we further demonstrate that MTBs are thermodynamically stable structures in Se-deficient sheets. These line defects host spatially localized states with energies close to the valence band minimum, thus giving rise to enhanced conductance along straight MTBs. However, electronic transport calculations show that the transmission of hole charge carriers across MTBs is strongly suppressed due to band bending effects. We further observe formation of MTBs during in situ removal of Se atoms by the electron beam of the microscope, thus confirming that MTBs appear due to Se-deficit, and not coalescence of individual grains during growth. At a very high local Se-deficit, the 2D sheet becomes unstable and transforms to a nanowire. Our results on Se-deficient MoSe2 suggest routes toward engineering the properties of 2D transition metal dichalcogenides by deviations from the stoichiometric composition.