As the Si counterpart of graphene, silicene may be defined as an at least partially sp2-hybridized, atom-thick honeycomb layer of Si that possesses π-electronic bands. Here we show that two-dimensional, epitaxial silicene forms through surface segregation on zirconium diboride thin films grown on Si wafers. A particular buckling of silicene induced by the epitaxial relationship with the diboride surface leads to a direct π-electronic band gap at the Γ point. These results demonstrate that the buckling and thus the electronic properties of silicene are modified by epitaxial strain.

The stability and electronic structure of competing silicene phases under in-plane compressive stress, either free-standing or on the ZrB 2 (0001) surface, has been studied by first-principles cal-3)-reconstructed structural modification was found to be stable on the ZrB 2 (0001) surface under epitaxial conditions. In contrast to the planar and buckled forms of free-standing silicene, in this "planar-like" phase, all but one of the Si atoms per hexagon reside in a single plane. While without substrate, for a wide range of strain, this phase is energetically less favorable than the buckled one, it is calculated to represent the ground state on the ZrB 2 (0001)surface. The atomic positions are found to be determined by the interactions with the nearest neighbor Zr atoms competing with Si-Si bonding interactions provided by the constraint of the honeycomb lattice.

The evolution of the electronic structure and the structural stability of epitaxial silicene on ZrB2(0001) thin films exposed to K atoms has been studied by angle-resolved photoelectron spectroscopy and low-energy electron diffraction. Potassium adsorption leads to charge donation to the silicene lattice, which is accompanied by the partial filling of a formerly unoccupied π* band and by the increasing hybridization between the diboride surface state and the lower branch of the back-folded π band. The results allow an identification of silicene-derived π electronic states and confirm that before K adsorption, the interactions at the silicene-substrate interface are rather weak.

So far, it represents a challenging task to reproduce angle-resolved photoelectron (ARPES) spectra of epitaxial silicene by first-principles calculations. Here, we report on the resolution of the previously controversial issue related to the structural configuration of silicene on the ZrB2(0001) surface and its band structure. In particular, by representing the band structure in a large Brillouin zone associated with a single Si atom, it is found that the imaginary part of the one-particle Green's function follows the spectral weight observed in ARPES spectra. By additionally varying the inplane lattice constant, the results of density functional theory calculations and ARPES data obtained in a wide energy range converge into the "planar-like" phase and provide the orbital character of electronic states in the vicinity of the Fermi level. It is anticipated that the choice of a smaller commensurate unit cell for the representation of the electronic structure will be useful for the study of epitaxial two-dimensional materials on various substrates in general.

The electronic structure of epitaxial, predominantly single-crystalline thin films of zirconium diboride (ZrB2), a lattice-matching, conductive ceramic to GaN, grown on Si(111) was studied using angle-resolved ultraviolet photoelectron spectroscopy. The existence of Zr-derived surface states dispersing along the Γ¯-M¯ direction indicates a metallic character provided by a two-dimensional Zr-layer at the surface. Together with the measured work function, the results demonstrate that the surface electronic properties of such thin ZrB2(0001) buffer layers are comparable to those of the single crystals promising excellent conduction between nitride layers and the substrate in vertical light-emitting diodes on economic substrates.

From the analysis of high-resolution Si 2p photoelectron and near-edge x-ray absorption fine structure (NEXAFS) spectra, we show that core level excitations of epitaxial silicene on ZrB2(0001) thin films are characteristically different from those of sp(3)-hybridized silicon. In particular, it is revealed that the lower Si 2p binding energies and the low onset in the NEXAFS spectra as well as the occurrence of satellite features in the core level spectra are attributed to the screening by low-energy valence electrons and interband transitions between π bands, respectively. The analysis of observed Si 2p intensities related to chemically distinct Si atoms indicates the presence of at least one previously unidentified component. The presence of this component suggests that the observation of stress-related stripe domains in scanning tunnelling microscopy images is intrinsically linked to the relaxation of Si atoms away from energetically unfavourable positions.

The interplay of sp 2 -and sp 3 -type bonding defines silicon allotropes in two-and three-dimensional forms. A two-dimensional phase bearing structural resemblance to a single MoS 2 layer is found to possess a lower total energy than low-buckled silicene and to be stable in terms of its phonon dispersion relations. A set of cigar-shaped nematic orbitals originating from the Si sp 2 orbitals realizes bonding with a sixfold coordination of the inner Si atoms of the layer. The identification of these nematic orbitals advocates diverse Si bonding configurations different from those of C atoms.

Epitaxial silicene, which forms spontaneously on ZrB2(0001) thin films grown on Si(111) wafers, has a periodic stripe domain structure. By adsorbing additional Si atoms on this surface, we find that the domain boundaries vanish, and a single-domain silicene sheet can be prepared without altering its buckled honeycomb structure. The amount of Si required to induce this change suggests that the domain boundaries are made of a local distortion of the silicene honeycomb lattice. The realization of a single domain sheet with structural and electronic properties close to those of the original striped state demonstrates the high structural flexibility of silicene.