Disruptive technologies are usually characterised by universal, versatile applications, which change many aspects of our life simultaneously, penetrating every corner of our existence. In order to become disruptive, a new technology needs to offer not incremental, but dramatic, orders of magnitude improvements. Moreover, the more universal the technology, the better chances it has for broad base success. Significant progress has been made in taking graphene and related materials from a state of raw potential to a point where they can revolutionize multiple industries. When it comes to electrochemical applications, Raman spectroscopy is an ideal non-destructive technique to study degradation in graphite anodes, as it is sensitive to doping, strain, defects, and interlayer coupling. I will discuss how in-situ Raman spectroscopy can unravel the signatures of Li-ion induced doping, intercalation staging and degradation upon cycling.
Vertically stacked two-dimensional (2D) heterostructures composed of 2D semiconductors have attracted great attention. Most of these include hexagonal boron nitride (h-BN) as either a substrate, an encapsulant, or a tunnel barrier. However, reliable synthesis of large-area and epitaxial 2D heterostructures incorporating BN remains challenging. Here, we demonstrate the epitaxial growth of nominal monolayer (ML) MoSe2 on h-BN/Rh(111) by molecular beam epitaxy, where the MoSe2/h-BN layer system can be transferred from the growth substrate onto SiO2. The valence band structure of ML MoSe2/h-BN/Rh(111) revealed by photoemission electron momentum microscopy ( kPEEM) shows that the valence band maximum located at the K point is 1.33 eV below the Fermi level ( EF), whereas the energy difference between K and Γ points is determined to be 0.23 eV, demonstrating that the electronic properties, such as the direct band gap and the effective mass of ML MoSe2, are well preserved in MoSe2/h-BN heterostructures.
Large-area hexagonal boron nitride (h-BN) promises many new applications of two-dimensional materials, such as the protective packing, of reactive surfaces or as membranes in liquids. However, scalable production beyond exfoliation from bulk single Crystals remained a major challenge. Single-orientation monolayer h-BN nanomesh is :grown, on 4 in. wafer single crystalline rhodium films and transferred on arbitrary substrates such as SiO2, germanium, or transmission electron microscopy grids. The transfer process involves application of tetraoctylammonium bromide before electrochemical hydrogen delamination. The material performance is demonstrated with two applications. First, protective sealing of h-BN is shown by preserving germanium from Oxidation in air at high temperatures. Second, the membrane functionality,of the single h-BN layer is demonstrated in aqueous solutions. Here, we employ a growth substrate intrinsic preparation scheme to create regular 2 nm holes that serve as ion channels in liquids.
The transport properties of graphene change strongly in the presence of electric fields due to graphene's band structure. This makes graphene sensitive to charges in an insulator substrate. Graphene on SiO2/Si is studied under x-ray irradiation in ambient conditions. Using the metal oxide semiconductor structure of their samples, the authors observe remote doping due to the creation of positive charges in the oxide by the irradiation and relate them to resistance and Hall effect measurements performed on the graphene gate. The observed changes in conductivity, Hall charge carrier density, and the corresponding charge carrier mobility are consistent with expectations as well as recent experiments using graphene field effect transistors under ultrahigh vacuum conditions [P. Procházka et al. Sci. Rep. 7, 563 (2017)]. Furthermore, the stability of the effect under ambient conditions and its recovery using thermal annealing is demonstrated.
We have deposited Sn on corrugated hexagonal boron nitride (h-BN) nanomeshs formed on Rh(111) and found that Sn atoms are intercalated between h-BN and Rh, flattening the h-BN. Our reflection high-energy electron diffraction (RHEED) analysis showed that the average in-plane lattice constant of h-BN increases due to the loss of the corrugation. Furthermore, electronic structure measurements based on angle-resolved photoemission spectroscopy (ARPES) showed that the h-BN a band width increases significantly while the a band width does not change as much. These behaviors were partly different from previous reports on the intercalation of h-BN/Rh system. Our results offer a novel, simple method to control the electronic structure of h-BN.
Large scale tetraoctylammonium-assisted electrochemical transfer of graphene grown on single-crystalline Ir(1 1 1) films by chemical vapour deposition is reported. The transferred samples are characterized in air with optical microscopy, Raman spectroscopy and four point transport measurements, providing the sheet resistance and the Hall carrier concentration. In vacuum we apply low energy electron diffraction and photoelectron spectroscopy that indicate transferred large-scale single orientation graphene. Angular resolved photoemission reveals a Fermi surface and a Dirac point energy which are consistent with charge neutral graphene.
The surface segregation profile of an intermetallic compound becomes vertically and laterally modulated upon epitaxial growth of a single-layer hexagonal boron nitride (h-BN) nanomesh. h-BN on PtRh(111) forms an 11-on-10 superhoneycomb, such as that on Rh(111) [Corso et al., Science 303, 217 (2004)], though with a smaller lattice constant of 2.73 nm. X-ray photoelectron diffraction shows that the h-BN layer reduces the Pt enrichment of the first layer by promoting site swapping of about 10 Pt-Rh pairs within the 10 x 10 unit cell between the first and second layers. This segregation profile is confirmed by density-functional-theory-based cluster-expansion calculations. Generally, a strong modulation of the h-BN bonding strength and a higher affinity to one of the constituents leads to self-assembly of top layer patches underneath the nanomesh pores.
The setup of an apparatus for chemical vapor deposition (CVD) of hexagonal boron nitride (h-BN) and its characterization on four-inch wafers in ultra high vacuum (UHV) environment is reported. It provides well-controlled preparation conditions, such as oxygen and argon plasma assisted cleaning and high temperature annealing. In situ characterization of a wafer is accomplished with target current spectroscopy. A piezo motor driven x-y stage allows measurements with a step size of 1 nm on the complete wafer. To benchmark the system performance, we investigated the growth of single layer h-BN on epitaxial Rh(111) thin films. A thorough analysis of the wafer was performed after cutting in atmosphere by low energy electron diffraction, scanning tunneling microscopy, and ultraviolet and X-ray photoelectron spectroscopies. The apparatus is located in a clean room environment and delivers high quality single layers of h-BN and thus grants access to large area UHV processed surfaces, which had been hitherto restricted to expensive, small area single crystal substrates. The facility is versatile enough for customization to other UHV-CVD processes, e.g., graphene on four-inch wafers.