Evidence for a diamondlike electronic band structure of Si multilayers on Ag(111)

Silicon multilayers on Ag(111) have been suggested to exhibit the structure of silicene, a material that has been heralded as a novel basis for microelectronic applications. However, our angle-resolved photoemission spectra (ARPES) from silicon multilayers on Ag(111) and of the silver-induced reconstruction of Si(111) demonstrate, from the close match in the valence level band structures, that the films exhibit a sp3 diamondlike structure. This refutes the interpretation o silicon multilayers on Ag(111) as silicene, a conclusion that is strengthened by the observation from core level photoemission that significant silver segregation occurs to the surface of these layers

An Artificially Lattice Mismatched Graphene/Metal Interface: Graphene/Ni/Ir(111)

We report the structural and electronic properties of an artificial graphene/Ni(111) system obtained by the intercalation of a monoatomic layer of Ni in graphene/Ir(111). Upon intercalation, Ni grows epitaxially on Ir(111), resulting in a lattice mismatched graphene/Ni system. By performing Scanning Tunneling Microscopy (STM) measurements and Density Functional Theory (DFT) calculations, we show that the intercalated Ni layer leads to a pronounced buckling of the graphene film. At the same time an enhanced interaction is measured by Angle-Resolved Photo-Emission Spectroscopy (ARPES), showing a clear transition from a nearly-undisturbed to a strongly-hybridized graphene $\pi$-band. A comparison of the intercalation-like graphene system with flat graphene on bulk Ni(111), and mildly corrugated graphene on Ir(111), allows to disentangle the two key properties which lead to the observed increased interaction, namely lattice matching and electronic interaction. Although the latter determines the strength of the hybridization, we find an important influence of the local carbon configuration resulting from the lattice mismatch.Comment: 9 pages, 3 figures, Accepted for publication in Phys. Rev.

Facile Electron Transfer in Atomically Coupled Heterointerface for Accelerated Oxygen Evolution

An efficient and cost-effective approach for the development of advanced cata-lysts has been regarded as a sustainable way for green energy utilization. The general guideline to design active and efficient catalysts for oxygen evolution reaction (OER) is to achieve high intrinsic activity and the exposure of more density of the interfacial active sites. The heterointerface is one of the most attractive ways that plays a key role in electrochemical water oxidation. Herein, atomically cluster-based heterointerface catalysts with strong metal support interaction (SMSI) between WMn2O4 and TiO2 are designed. In this case, the WMn2O4 nanoflakes are uniformly decorated by TiO2 particles to create electronic effect on WMn2O4 nanoflakes as confirmed by X-ray absorption near edge fine structure. As a result, the engineered heterointerface requires an OER onset overpotential as low as 200 mV versus reversible hydrogen electrode, which is stable for up to 30 h of test. The outstanding performance and long-term durability are due to SMSI, the exposure of interfacial active sites, and accelerated reaction kinetics. To confirm the synergistic interaction between WMn2O4 and TiO2, and the modification of the electronic structure, high-resolution transmission electron microscopy (HR-TEM), X-ray photoemission spectroscopy (XPS), and X-ray absorption spectroscopy (XAS) are used

Correlated Electrons Step-by-Step: Itinerant-to-Localized Transition of Fe Impurities in Free-Electron Metal Hosts

High-resolution photoemission spectroscopy and realistic ab-initio calculations have been employed to analyze the onset and progression of d-sp hybridization in Fe impurities deposited on alkali metal films. The interplay between delocalization, mediated by the free-electron environment, and Coulomb interaction among d-electrons gives rise to complex electronic configurations. The multiplet structure of a single Fe atom evolves and gradually dissolves into a quasiparticle peak near the Fermi level with increasing the host electron density. The effective multi-orbital impurity problem within the exact diagonalization scheme describes the whole range of hybridizations.Comment: 10 pages, 4 figure

Low-temperature insulating phase of the Si(111)–7×7 surface

We investigated the electronic structure of the Si(111)-7 x 7 surface below 20 K by scanning tunneling and photoemission spectroscopies and by density functional theory calculations. Previous experimental studies have questioned the ground state of this surface, which is expected to be metallic in a band picture because of the odd number of electrons per unit cell. Our differential conductance spectra instead show the opening of an energy gap at the Fermi level and a significant temperature dependence of the electronic properties, especially for the adatoms at the center of the unfaulted half of the unit cell. Complementary photoemission spectra with improved correction of the surface photovoltage shift corroborate the differential conductance data and demonstrate the absence of surface bands crossing the Fermi level at 17 K. These consistent experimental observations point to an insulating ground state and contradict the prediction of a metallic surface obtained by density functional theory in the generalized gradient approximation. The calculations indicate that this surface has or is near a magnetic instability, but remains metallic in the magnetic phases even including correlation effects at mean-field level. We discuss possible origins of the observed discrepancies between experiments and calculations

Absence of Dirac cones in monolayer silicene and multilayer Si films on Ag(111)

Monolayer silicene and multilayer silicon films on Ag(111) have been the subject of many investigations within the last few years. For both systems, photoemission data have been interpreted in terms of linearly dispersing bands giving rise to the characteristic Dirac cone features, similar to graphene. Here we demonstrate, on the basis of angle-resolved valence band and core level photoemission data that this assignment is not correct. The bands previously attributed to states with Dirac fermion character are shown to derive from Ag(111) interface and bulk states in the silicene monolayer and from the well-known Ag-View the MathML source(3×3)R30°-Si(111) structure in Si multilayers. These results question the validity of the claim that graphene-like silicene and silicene multilayers are in fact formed on Ag(111)

Synchrotron radiation photoemission spectroscopy of the oxygen modified CrCl3 surface

We investigate the experimentally challenging CrCl3 surface by photon energy dependent photoemission (PE). The core and valence electrons after cleavage of a single crystal, either in a ultra-high vacuum (UHV) or in air, are studied by keeping the samples at 150 degrees C, aiming at confirming the atomic composition with respect to the expected bulk atomic structure. A common spectroscopic denominator revealed by data is the presence of a stable, but only partially ordered Cl-O-Cr surface. The electronic core levels (Cl 2p, Cr 2p and 3p), the latter ones of cumbersome component determination, allowed us to quantify the electron charge transfer to the Cr atom as a net result of this modification and the increased exchange interaction between metal and ligand atoms. In particular, the analysis of multiplet components by the CMT4XPS code evidenced the charge transfer to be favored, and similarly the reduced crystal field due to the established polarization field. Though it is often claimed that a significant amount of Cl and Cr atomic vacancies has to be included, such a possibility can be excluded on the basis of the sign and the importance of the shift in the binding energy of core level electrons. The present methodological approach can be of great impact to quantify the structure of ordered sub-oxide phases occurring in mono or bi-layer Cr trihalides