Field Assisted Reactive Gas Etching of Multiple Tips Observed using FIM.

A simple and cost effective method to fabricate multiple tungsten (W) single atom tips (SATs) from both poly and single crystalline wires is reported. Two or four tips attached to a holder are electrochemically etched together in NaOH solution followed by a controlled field assisted reactive gas etching in vacuum using nitrogen as an etching gas and helium as an imaging gas. A Common high voltage is applied simultaneously to all nanotips to shape the apexes towards single atoms. Single atom tips were achieved for both W(111) and W(110) while trimer tips were also achieved for W(111). This observation can lead to an important step towards realizing simplified etching processes of multiple tips which in turn can help to simultaneously fabricate numerous tips leading to mass fabrication and characterization.

Quantitative Multilayer Cu(410) Structure and Relaxation Determined by QLEED.

Industrially relevant catalytically active surfaces exhibit defects. These defects serve as active sites; expose incoming adsorbates to both high and low coordinated surface atoms; determine morphology, reactivity, energetics, and surface relaxation. These, in turn, affect crystal growth, oxidation, catalysis, and corrosion. Systematic experimental analyses of such surface defects pose challenges, esp., when they do not exhibit order. High Miller index surfaces can provide access to these features and information, albeit indirectly. Here, we show that with quantitative low-energy electron diffraction (QLEED) intensity analyses and density functional theory (DFT) calculations, we can visualize the local atomic configuration, the corresponding electron distribution, and local reactivity. The QLEED-determined Cu(410) structure (Pendry reliability factor RP ≃ 0.0797) exhibits alternating sequences of expansion (+) and contraction (-) (of the first 16 atomic interlayers) relative to the bulk-truncated interlayer spacing of ca. 0.437 Å. The corresponding electron distribution shows smoothening relative to the bulk-determined structure. These results should aid us to further gain an atomic-scale understanding of the nature of defects in materials.

Epitaxial chemical vapour deposition growth of monolayer hexagonal boron nitride on a Cu(111)/sapphire substrate.

Hexagonal boron nitride (h-BN), an atomically thin insulating material, shows a large band gap, mechanical flexibility, and optical transparency. It can be stacked with other two-dimensional (2D) materials through van der Waals interactions to form layered heterostructures. These properties promise its application as an insulating layer of novel 2D electronic devices due to its atomically smooth surface with a large band gap. Herein, we demonstrated the ambient-pressure chemical vapour deposition (CVD) growth of high-quality, large-area monolayer h-BN on a Cu(111) thin film deposited on a c-plane sapphire using ammonia borane (BH3NH3) as the feedstock. Highly oriented triangular h-BN grains grow on Cu(111), which finally coalescence to cover the entire Cu surface. Low-energy electron diffraction (LEED) measurements indicated that the hexagonal lattice of the monolayer h-BN is well-oriented along the underlying Cu(111) lattice, thus implying the epitaxial growth of h-BN, which can be applied in various 2D electronic devices.

Effects of Pb Intercalation on the Structural and Electronic Properties of Epitaxial Graphene on SiC.

The effects of Pb intercalation on the structural and electronic properties of epitaxial single-layer graphene grown on SiC(0001) substrate are investigated using scanning tunneling microscopy (STM), noncontact atomic force microscopy, Kelvin probe force microscopy (KPFM), X-ray photoelectron spectroscopy, and angle-resolved photoemission spectroscopy (ARPES) methods. The STM results show the formation of an ordered moiré superstructure pattern induced by Pb atom intercalation underneath the graphene layer. ARPES measurements reveal the presence of two additional linearly dispersing π-bands, providing evidence for the decoupling of the buffer layer from the underlying SiC substrate. Upon Pb intercalation, the Si 2p core level spectra show a signature for the existence of PbSi chemical bonds at the interface region, as manifested in a shift of 1.2 eV of the bulk SiC component toward lower binding energies. The Pb intercalation gives rise to hole-doping of graphene and results in a shift of the Dirac point energy by about 0.1 eV above the Fermi level, as revealed by the ARPES measurements. The KPFM experiments have shown that decoupling of the graphene layer by Pb intercalation is accompanied by a work function increase. The observed increase in the work function is attributed to the suppression of the electron transfer from the SiC substrate to the graphene layer. The Pb intercalated structure is found to be stable in ambient conditions and at high temperatures up to 1250 °C. These results demonstrate that the construction of a graphene-capped Pb/SiC system offers a possibility of tuning the graphene electronic properties and exploring intriguing physical properties such as superconductivity and spintronics.

Catalytic Growth of Graphene: Toward Large-Area Single-Crystalline Graphene.

For electronic applications, synthesis of large-area, single-layer graphene with high crystallinity is required. One of the most promising and widely employed methods is chemical vapor deposition (CVD) using Cu foil/film as the catalyst. However, the CVD graphene is generally polycrystalline and contains a significant amount of domain boundaries that limit intrinsic physical properties of graphene. In this Perspective, we discuss the growth mechanism of graphene on a Cu catalyst and review recent development in the observation and control of the domain structure of graphene. We emphasize the importance of the growth condition and crystallinity of the Cu catalyst for the realization of large-area, single-crystalline graphene.

Epitaxial chemical vapor deposition growth of single-layer graphene over cobalt film crystallized on sapphire.

Epitaxial chemical vapor deposition (CVD) growth of uniform single-layer graphene is demonstrated over Co film crystallized on c-plane sapphire. The single crystalline Co film is realized on the sapphire substrate by optimized high-temperature sputtering and successive H(2) annealing. This crystalline Co film enables the formation of uniform single-layer graphene, while a polycrystalline Co film deposited on a SiO(2)/Si substrate gives a number of graphene flakes with various thicknesses. Moreover, an epitaxial relationship between the as-grown graphene and Co lattice is observed when synthesis occurs at 1000 °C; the direction of the hexagonal lattice of the single-layer graphene completely matches with that of the underneath Co/sapphire substrate. The orientation of graphene depends on the growth temperature and, at 900 °C, the graphene lattice is rotated at 22 ± 8° with respect to the Co lattice direction. Our work expands a possibility of synthesizing single-layer graphene over various metal catalysts. Moreover, our CVD growth gives a graphene film with predefined orientation, and thus can be applied to graphene engineering, such as cutting along a specific crystallographic direction, for future electronics applications.

Epitaxial silicon oxynitride layer on a 6H-SiC(0001) surface.

Hydrogen-gas etching of a 6H-SiC(0001) surface and subsequent annealing in nitrogen atmosphere leads to the formation of a silicon oxynitride (SiON) epitaxial layer. A quantitative low-energy electron diffraction analysis revealed that the SiON layer has a hetero-double-layer structure: a silicate monolayer on a silicon nitride monolayer via Si-O-Si bridge bonds. There are no dangling bonds in the unit cell, which explains the fact that the structure is robust against air exposure. Scanning tunneling spectroscopy measured on the SiON layer shows a bulk SiO2-like band gap of approximately 9 eV. Great potential of this new epitaxial layer for device applications is described.

Electron-beam-induced disordering of the Si(001)-c(4 x 2) surface structure.

An electron beam (EB) irradiation effect on the Si(001)-c(4 x 2) surface was investigated by using low-energy electron diffraction. Quarter-order spots become dim and streaky by EB irradiation below approximately 40 K, indicating a disordering in the c(4 x 2) arrangement of buckled dimers. A quantitative analysis of decreasing rates of the spot intensity at various conditions of beam current, beam energy, and substrate temperature leads to a proposal for a mechanism of the disordering in the buckled-dimer arrangement in terms of electronic excitation, electron-phonon coupling, and carrier concentration.