Two-dimensional transition metal dichalcogenides (TMDs) are promising low-dimensional materials which can produce diverse electronic properties and band alignment in van der Waals heterostructures. Systematic density functional theory (DFT) calculations are performed for 24 different TMD monolayers and their bilayer heterostacks. DFT calculations show that monolayer TMDs can behave as semiconducting, metallic or semimetallic depending on their structures; we also calculated the band alignment of the TMDs to predict their alignment in van der Waals heterostacks. We have applied the charge equilibration model (CEM) to obtain a quantitative formula predicting the highest occupied state of any type of bilayer TMD heterostacks (552 pairs for 24 TMDs). The CEM predicted values agree quite well with the selected DFT simulation results. The quantitative prediction of the band alignment in the TMD heterostructures can provide an insightful guidance to the development of TMD-based devices.

Metal-insulator transitions in low-dimensional materials under ambient conditions are rare and worth pursuing due to their intriguing physics and rich device applications. Monolayer MoTe2 and WTe2 are distinguished from other TMDs by the existence of an exceptional semimetallic distorted octahedral structure (T') with a quite small energy difference from the semiconducting H phase. In the process of transition metal alloying, an equal stability point of the H and the T' phase is observed in the formation energy diagram of monolayer WxMo1-xTe2. This thermodynamically driven phase transition enables a controlled synthesis of the desired phase (H or T') of monolayer WxMo1-xTe2 using a growth method such as chemical vapor deposition (CVD) and molecular beam epitaxy (MBE). Furthermore, charge mediation, as a more feasible method, is found to make the T' phase more stable than the H phase and induce a phase transition from the H phase (semiconducting) to the T' phase (semimetallic) in monolayer WxMo1-xTe2 alloy. This suggests that a dynamic metal-insulator phase transition can be induced, which can be exploited for rich phase transition applications in two-dimensional nanoelectronics.

We performed first-principles calculations to investigate the hydrogen storage characteristics of carbon-based 3-D solid structures, called covalently bonded graphenes (CBGs). Using the density functional method and the Møller-Plesset perturbation method, we show that H2 molecular binding in the CBGs is stronger than that on an isolated graphene with an increase of 20 to approximately 150% in binding energy, which is very promising for storage at ambient conditions. We also suggest that the CBGs of appropriate size can effectively work as frameworks for transition metal dispersion. The adsorption properties of hydrogen on the metal atoms dispersed inside the CBGs are also presented.

We report the fabrication of nanocrystalline graphite films on sapphire substrates of various cutting directions by using solid carbon source molecular beam epitaxy. Raman spectra show a systematic change from amorphous carbon to nanocrystalline graphite with a cluster diameter of several nanometers, depending on the growth temperature. The symmetry of the substrate seems to have little effect on the film quality. Simulations suggest that the strong bonding between carbon and oxygen may lead to orientational disorders. Transport measurements show a Dirac-like peak and a carrier type change by the gate voltage.

A periodically modulated graphene (PMG) generated by nanopatterned surfaces is reported to profoundly modify the intrinsic electronic properties of graphene. The temperature dependence of the sheet resistivity and gate response measurements clearly show a semiconductor-like behavior. Raman spectroscopy reveals significant shifts of the G and the 2D modes induced by the interaction with the underlying grid-like nanostructure. The influence of the periodic, alternating contact with the substrate surface was studied in terms of strain caused by bending of graphene and doping through chemical interactions with underlying substrate atoms. Electronic structure calculations performed on a model of PMG reveals that it is possible to tune a band gap within 0.14-0.19 eV by considering both the periodic mechanical bending and the surface coordination chemistry. Therefore, the PMG can be regarded as a further step toward band gap engineering of graphene devices.

The adsorption of pyridine onto the Ge(100) surface has been studied using both real-time scanning tunneling microscopy (STM) and ab initio pseudopotential density functional calculations. The results show that pyridine molecules adsorb on the electron-deficient down-Ge atoms of the Ge=Ge dimers via Ge-N dative bonding, with the pyridine ring tilted to the surface. The electron-rich up-Ge atoms remaining after adsorption of pyridine induce an asymmetric dimer row, which is mainly reconstructed to the c(4 x 2) structure. At pyridine coverage of 0.25 ML, the adsorbed pyridine molecules form a perfectly ordered monolayer. The entire Ge substrate underlying this organic monolayer rearranges into the c(4 x 2) structure.

The production of holes by electron beam irradiation in hexagonal boron nitride (hBN), which has a lattice similar to that of graphene, is monitored over time using atomic resolution transmission electron microscopy. The holes appear to be initiated by the formation of a vacancy of boron and grow in a manner that retains an overall triangular shape. The hole growth process involves the formation of single chains of B and N atoms and is accompanied by the ejection of atoms and bundles of atoms along the hole edges, as well as atom migration. These observations are compared to density functional theory calculations and molecular dynamics simulations.

We investigated the surface potential (V surf ) of exfoliated MoS 2 flakes on bare and Au-coated SiO 2 /Si substrates using Kelvin probe force microscopy. The V surf of MoS 2 single layers was larger on the Au-coated substrates than on the bare substrates; our theoretical calculations indicate that this may be caused by the formation of a larger electric dipole at the MoS 2 / Au interface leading to a modified band alignment. V surf decreased as the thickness of the flakes increased until reaching the bulk value at a thickness of ∼20 nm (∼30 layers) on the bare and ∼80 nm (∼120 layers) on the Au-coated substrates, respectively. This thickness dependence of V surf was attributed to electrostatic screening in the MoS 2 layers. Thus, a difference in the thickness at which the bulk V surf appeared suggests that the underlying substrate has an effect on the electric-field screening length of the MoS 2 flakes. This work provides important insights to help understand and control the electrical properties of metal/MoS 2 contacts.