Image potential states at transition metal oxide surfaces: A time-resolved two-photon photoemission study on ultrathin NiO films

For well-ordered ultrathin films of NiO(001) on Ag(001), a series of unoccupied states below the vacuum level has been found. The states show a nearly free electron dispersion and binding energies which are typical for image potential states. By time-resolved two-photon photoemission (2PPE), the lifetimes of the first three states and their dependence on oxide film thickness are determined. For NiO film thicknesses between 2 and 4 monolayers (ML), the lifetime of the first state is in the range of 28–42 fs and shows an oscillatory behavior with increasing thickness. The values for the second state decrease monotonically from 88 fs for 2 ML to 33 fs for 4 ML. These differences are discussed in terms of coupling of the unoccupied states to the layer-dependent electronic structure of the growing NiO film

Electron pair emission from surfaces: some general experimental considerations

We discuss some experimental facets of electron pair emission from surfaces using two different experimental approaches. In the first case the instrument consists of a pair of hemispherical analyzers which are operated with continuous primary beams of electrons or photons. The second instrument employs a pair of time-of-flight spectrometers which require a pulsed excitation source. A key experimental quantity is the ratio of ‘true’ to ‘random’ coincidences which can be determined in different ways. Regardless of the type of instrument the primary flux has to adopt a much smaller value than in single electron spectroscopy. We describe different approaches to obtain the relevant count rates, in particular the concept of operating with a delayed coincidence circuit. We also address the question on how to compare the two types of spectrometer in terms of their performance

Extended energy range analysis for angle-resolved time-of-flight photoelectron spectroscopy

An approximation method for electrostatic time-of-flight (ToF) spectroscopy on photoelectrons distributed over a wide energy range is presented. This method is an extension of conventional analysis and aims at specific energy and angular regions, where distinctly different emission angles and energies are mapped to the same ToF and detector position by the spectrometer. The general formulation and the systematic errors are presented, and a practical example is demonstrated for photoelectrons from Ag(001) with kinetic energies of 0.5–25 eV

Full real-space analysis of a dodecagonal quasicrystal

The atomically resolved real-space structure of a long-range-ordered dodecagonal quasicrystal is determined based on scanning tunnelling microscopy. For the BaTiO3-derived oxide quasicrystal which spontaneously forms on a Pt(111) surface, 8100 atomic positions have been determined and are compared with an ideal Niizeki–Gähler tiling. Although the Niizeki–Gähler tiling has a complex three-element structure, the abundance of the triangle, square and rhomb tiling elements in the experimental data closely resembles the ideal frequencies. Similarly, the frequencies of all possible next-neighbour tiling combinations are, within the experimental uncertainty, identical to the ideal tiling. The angular and orientational distributions of all individual tiling elements show the characteristics of the dodecagonal quasicrystal. In contrast, the analysis of the orientation of characteristic and more complex tiling combinations indicates the partial decomposition of the quasicrystal into small patches with locally reduced symmetry. These, however, preserve the long-range quasicrystal coherence. The symmetry reduction from dodecagonal to sixfold is assigned to local interaction with the threefold substrate. It leads to atomic flips which preserve the number of quasicrystal tiling elements

Surface stress and lattice dynamics in oxide ultrathin films

The lattice misfit between the substrate and an epitaxial film leads in general to static forces, which define the interface stress, and dynamic responses that modify the thin-film lattice dynamics. Although these are both fundamental concepts that are important for film growth and thin-film properties, they have not been investigated in a combined way so far. Therefore, herein, surface stress experiments in combination with surface phonon studies for three different, cubic oxide ultrathin film systems are reviewed. Within the class of binary oxides, NiO(001) grown on Ag(001) is chosen, which exhibits a -2.2% lattice mismatch, and BaO(001) on Pt(001), a system with a negligible lattice mismatch. For the ternary oxides, perovskite thin films of BaTiO3 grown epitaxially on Pt(001) with a lattice mismatch of -2.3% are focused upon. The surface stress experiments are conducted with an optical two-beam curvature technique under in situ growth conditions. Surface and thin-film phonons are determined by high-resolution electron energy loss spectroscopy. Surface stress and lattice dynamics are discussed in the range from the oxide monolayer to thin films of about 20 unit cell in thickness

2D honeycomb transformation into dodecagonal quasicrystals driven by electrostatic forces

Dodecagonal oxide quasicrystals are well established as examples of long-range aperiodic order in two dimensions. However, despite investigations by scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), low-energy electron microscopy (LEEM), photoemission spectroscopy as well as density functional theory (DFT), their structure is still controversial. Furthermore, the principles that guide the formation of quasicrystals (QCs) in oxides are elusive since the principles that are known to drive metallic QCs are expected to fail for oxides. Here we demonstrate the solution of the oxide QC structure by synchrotron-radiation based surface x-ray diffraction (SXRD) refinement of its largest-known approximant. The oxide QC formation is forced by large alkaline earth metal atoms and the reduction of their mutual electrostatic repulsion. It drives the n = 6 structure of the 2D Ti2O3 honeycomb arrangement via Stone–Wales transformations into an ordered structure with empty n = 4, singly occupied n = 7 and doubly occupied n = 10 rings, as supported by DFT