Thin manganese silicide films of different thicknesses on Si(111) have been studied in detail by low-energy electron diffraction (LEED), scanning tunneling microscopy, and scanning tunneling spectroscopy (STM/STS). Up to a Mn coverage of 3–4 monolayers (ML), island formation is favored. For higher Mn coverages up to 12 ML uniform film growth is found. The silicide film morphology at low coverages supports a layered Mn-Si film structure. The silicide surfaces displayed a √3×√3 LEED pattern. STM images recorded from the √3×√3 surfaces mostly show a hexagonal pattern but a honeycomb pattern has also been observed. A surface atomic structure based on chained Mn triangles is proposed. Our STM results are in good agreement with a recent theoretical model. The high-quality STS spectra recorded from the different surfaces show a clear metallic character at 1.5 ML and higher coverages. The filled-state features in the STS spectra at surfaces with 3–4 ML Mn coverages are similar to earlier published angle-resolved photoelectron spectroscopy data.
Thin manganese germanide films with different thicknesses on Ge(111) have been studied in detail by low-energy electron diffraction (LEED), scanning tunneling microscopy, and core-level spectroscopy (CLS). Annealing of the deposited Mn on Ge(111)c(2×8) between 330-450 C resulted in well-ordered Mn5Ge3 surfaces as seen by intense 3×3 LEED spots. Up to a coverage of 24 monolayers (ML), island formation is favored. At a coverage of 32 ML a well ordered Mn5Ge3 film was found to fully cover the surface. High-resolution Ge 3d CLS spectra were recorded with photon energies between 50 and 110 eV at normal and 60 emission angles. In contrast to earlier results, three components have been used in the line-shape analysis to achieve a consistent fit over the energy and angular range. In addition, three components have been identified for the Mn 2p CLS spectra. The two major components fit well with a layered Mn germanide structure suggested in the literature.
The atomic and electronic structure of the Mn5Ge3(001) surface grown on Ge(111) c(2×8) has been studied in detail by angle-resolved photoelectron spectroscopy (ARPES), scanning tunneling microscopy (STM), and scanning tunneling spectroscopy. ARPES spectra recorded from the Γ̅ -K̅ -M̅ and Γ̅ -M̅ -Γ̅ directions of the surface Brillouin zone show six surface-related features. The STM images recorded at biases higher/lower than ±0.4 V always show a honeycomb pattern with two bright protrusions in each unit cell. At lower biases, a hexagonal, intermediate transition, and a honeycomb pattern are observed. These can be explained as arising from Mn and Ge atoms in the sublayer arranged in triangular structures and Mn atoms in the top layer arranged in a honeycomb structure, respectively. The photoemission and STM data from the germanide surface are discussed and compared to earlier published theoretical, photoelectron spectroscopy, and scanning tunneling microscopy studies.
The Mn/Si(111)-√3×√3 surface has been studied in detail by low energy electron diffraction (LEED), angle-resolved photoelectron spectroscopy (ARPES), and core-level photoelectron spectroscopy (CLS). Annealing of the deposited manganese resulted in a well-ordered surface as seen by intense √3×√3 LEED spots. ARPES spectra recorded in the Γ̅ -K̅ -M̅ direction of the √3×√3 surface Brillouin zone show five surface related features in the band gap while in the Γ̅ -M̅ -Γ̅ direction four surface features are observed. The high-resolution Si 2p CLS data were recorded at photon energies between 108–140 eV both at normal and 60° emission angle. The bulk component was identified from the bulk sensitive spectrum recorded at a photon energy of 108 eV. To achieve a consistent core-level fitting over the whole energy and angular range, five components were introduced in the line-shape analysis. The photoemission data from the √3×√3 surface have been discussed and compared with a recent theoretical model. The findings here support a layered Mn silicide film structure.
Several promising applications of amorphous titanium dioxide, aTiO2, have appeared recently, but thecorrelation between electronic properties and atomic short-range structural order is poorly understood. Herein weshow that structural disorder yields local undercoordinated TiOx units which influence electronic hybridization ofTi-[4p] andTi-[3d] orbitals with a lowcrystal-field splitting [E(eg)-E(t2g) = 2.4 ± 0.3 eV]. The short-range orderand electronic properties of aTiO2 thin-film oxides are described through an integrated approach based on x-rayabsorptionexperiments and ab initio computational simulations where the energy splitting of the electronic levelsin the Ti-[4p-3d]manifold are analyzed. Structural disorder provides enough p-d orbitalmixing for the hybridizedelectronic transitions from the Ti-[1s] core level into the [Ti-t2g] and [Ti-eg] bands [1s → 4p-3d excitations],to be allowed. This yields an intense pre-edge structure in the Ti K-edge x-ray-absorption near-edge structurespectrum of aTiO2, which is consistent with the projected density of states on the photoabsorbing Ti atoms.
The electronic structures of the Sn/Si(111)-2√3×2√3 surface and deposited 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) have been studied by use of high-resolution photoelectron spectroscopy and scanning tunneling microscopy. On deposition, PTCDA molecules form a 4√3×2√3 periodicity superposed on the substrate. The new reconstruction is caused by a charge transfer between the Sn/Si(111)-2√3×2√3 surface and the molecules, as indicated by a new component of the Sn 4d core level that is shifted toward higher binding energy. In contrast to earlier reports, the charge provided by Sn is given to carbonyl C atoms instead of O atoms. This is evidenced by a new component in the C 1s core-level spectra, which is shifted toward lower binding energy. The charge transfer also induces a splitting in the highest occupied molecular orbital level of PTCDA seen in the valence band structure.
The electronic structures of PTCDA films on Sn/Si(111)-√3×√3 have been studied by high-resolution photoelectron spectroscopy (PES) and near-edge x-ray absorption fine structure (NEXAFS). There is a clear chemical interaction between PTCDA molecules and the Sn/Si(111)-√3×√3 surface, as indicated by new components in Sn 4d core levels that are shifted to higher binding energies. The chemical interaction is also evidenced by new components in the O-1s and C-1s core-level spectra. The new components are shifted to lower binding energies and have their origins from two reactions between Sn dangling bonds and the PTCDA molecules. One reaction is located at the anhydride O atom and the other is at the carbonyl C atom. These reactions also induce modifications in the HOMO and LUMO levels seen in the valence band and NEXAFS spectra. For thin films, the NEXAFS results suggest a tilting molecular configuration with respect to the substrate, while for the thicker films, there is an improved ordering of the molecular orientation to the substrate.
Thin Mn germanide films with nanoscale thicknesses on Ge(111) have been studied by low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), core-level spectroscopy (CLS), and x-ray magnetic circular dichroism. The 260 ∘C annealing of 16 monolayers of Mn deposited on Ge(111)c(2×8) resulted in a uniform film with intense threefold split √3×√3 LEED spots and Moiré patterns in the STM images. This ultrathin film shows a clear ferromagnetism with a Curie temperature of ∼250 K. High-resolution Ge 3d CLS spectra were recorded with photon energies between 50 and 90 eV at normal and 60∘ emission angle. To achieve a consistent fit over the energy and angular range three components were used in the line-shape analysis. The low temperature (260 ∘C) annealed film shows significant differences in terms of electronic structure and magnetism in contrast to the high temperature (330 ∘C or above) annealed ones. Our results indicate that the annealing temperature and the Mn coverage play important roles in the formation of a thin magnetic Mn germanide film.