Katariina Pussi

Structure and local variations of the graphene moiré on Ir(111)

We have studied the incommensurate moire structure of epitaxial graphene grown on iridium(111) by dynamic low-energy electron diffraction [LEED I(V)] and noncontact atomic force microscopy (AFM) with a CO-terminated tip. Our LEED I(V) results yield the average positions of all the atoms in the surface unit cell and are in qualitative agreement with the structure obtained from density functional theory. The AFM experiments reveal local variations of the moire structure: The corrugation varies smoothly over several moire unit cells between 42 and 56 pm. We attribute these variations to the varying registry between the moire symmetry sites and the underlying substrate. We also observe isolated outliers, where the moire top sites can be offset by an additional 10 pm. This study demonstrates that AFM imaging can be used to directly yield the local surface topography with pm accuracy even on incommensurate two-dimensional structures with varying chemical reactivity.

The evolution of the electronic structure at the Bi/Ag(111) interface studied using photoemission spectroscopy

The growth of Bi on Ag(111) induces different surface structures, including (√3 × √3)R30° surface alloy, Bi-(p × √3) overlayer and Bi(110) thin film, as a function of increasing Bi coverage. Here we report the study of electronic states of these structures using core level and valence band photoemission spectroscopy at room temperature. The sp-derived Shockley surface state on Ag(111) is rapidly quenched upon deposition of Bi, due to the strong variation of the in-plane surface potential in the Ag(2)Bi surface alloy. The Bi 4f core levels of the (√3 × √3)R30° alloy and Bi(110) thin film are shifted to lower binding energy by ~0.6 eV and ~0.3 eV compared with the Bi bulk value, respectively. Mechanisms inducing the core level shifts are discussed as due to a complex superposition of several factors. As Bi coverage increases and a Bi(110) overlayer forms on Ag(111), a new state is observed at ~0.9 ML arising from electronic states localized at the Ag-Bi interface. Finally the change of work function as a function of coverage is discussed on the basis of a charge transfer model.

LEED analysis of the surface structure of decagonal Al–Co–Ni using its W-approximant as a model structure

Abstract The analysis of low-energy electron diffraction (LEED) intensities from quasicrystal surfaces requires the use of periodic model structures that contain the same structure features as the quasicrystal. In this paper, we present the analysis of LEED data from 10-fold decagonal Al–Co–Ni using the W approximant structure as the model. A preference was found for an Al-rich termination of the surface, with very little relaxation of the surface planes relative to the bulk structure. This result is similar to the results of an ab inito calculation of a similar surface structure [1]. The results are compared from earlier analyses of the same data using different structure models [2].

A novel method for the extraction of intensity–energy spectra from low-energy electron diffraction patterns

Abstract Low-energy electron diffraction is an important technique in surface science. The first step in the analysis of experimental data is the extraction of intensity–energy spectra from a series of diffraction images. In this paper, we describe a novel method for an automatic extraction of these spectra based on Kalman filtering. The algorithm combines the knowledge about the movement of the diffraction maxima with spot detection. We show successful implementation of the proposed method using simulated and real data.

Structure of the SnO2(110)-(4 × 1) surface

Using surface x-ray diffraction (SXRD), quantitative low-energy electron diffraction (LEED), and density-functional theory (DFT) calculations, we have determined the structure of the (4×1) reconstruction formed by sputtering and annealing of the SnO_{2}(110) surface. We find that the reconstruction consists of an ordered arrangement of Sn_{3}O_{3} clusters bound atop the bulk-terminated SnO_{2}(110) surface. The model was found by application of a DFT-based evolutionary algorithm with surface compositions based on SXRD, and shows excellent agreement with LEED and with previously published scanning tunneling microscopy measurements. The model proposed previously consisting of in-plane oxygen vacancies is thus shown to be incorrect, and our result suggests instead that Sn(II) species in interstitial positions are the more relevant features of reduced SnO_{2}(110) surfaces.

Low-Energy Electron Diffraction (LEED) Study of an Aperiodic Thin Film of Cu on 5-fold i-Al-Pd-Mn

Thin films of copper grown on five-fold i-AlPdMn at room temperature consist of domains that are rotationally aligned with the five primary symmetry directions of the substrate and which have one-dimensional aperiodic order. This aperiodic order is evident in scanning tunnelling microscopy images as wide and narrow rows that are spaced according to a Fibonacci sequence. A low-energy electron diffraction (LEED) study of this film indicates that the structure within the domains is periodic along the rows, with a repeat distance equal to the nearest-neighbour separation in bulk Cu. To determine the complete structure, a dynamical LEED experiment was performed for a five-layer Cu film at a sample temperature of 85 K. The analysis was performed using two different computational methods, one based on quasicrystalline slabs and the other on periodic approximants. Of the model structures tested, the film is found to be most consistent with a structure based on the Cu{100} surface structure, but having aperiodic displacements, both in-plane and out-of-plane, along a ⟨110⟩ direction.

Low-energy electron diffraction and density functional theory study of potassium adsorbed on Pb(1 0 0)

Alkali metal adsorption systems provide important models for chemisorption. Low-energy electron diffraction experiments and density functional theory calculations were carried out for the adsorption of potassium on Pb(1 0 0). The stable structure for all submonolayer coverages was found to be the commensurate c(2   ×   2) structure, with potassium atoms located in substitutional sites in the top substrate layer. This structure is temperature activated and occurs for adsorption or annealing of the film above 200 K. This finding is consistent with an earlier theory that proposed that for substrates with low energies of vacancy formation, substitutional structures can be the most stable. The structural and vibrational parameters deduced from the experiment are in agreement with the calculated values, and these values fit well into and add to the database of alkali metal adsorption properties.

Correlation of electron self-energy with geometric structure in low-energy electron diffraction

In low-energy electron diffraction (LEED) studies of surface geometries where the energy dependence of the intensities is analyzed, the in-plane lattice parameter of the surface is usually set to a value determined by x-ray diffraction for the bulk crystal. In cases where it is not known, for instance in films that are incommensurate with the substrate, it is desirable to fit the in-plane lattice parameters in the same analysis as the perpendicular interlayer spacings. We show that this is not possible in a conventional LEED I(E) analysis because the inner potential, which is typically treated as an adjustable parameter, is correlated with the geometrical structure. Therefore, without having prior knowledge of the inner potential, it is not possible to determine the complete surface structure simply from LEED I(E) spectra, and the in-plane lattice parameter must be determined independently before the I(E) analysis is performed. This can be accomplished by establishing a more precise experimental geometry. Further, it is shown that the convention of omitting the energy dependency of the real part of the inner potential means geometrical LEED results cannot be trusted beyond a precision of approximately 0.01 Å.

LEED I–V and DFT structure determination of the (\surd 3\times \surd 3)\mathrm{R}30^{\circ } Pb–Ag(111) surface alloy

The deposition of 1/3 of a monolayer of Pb on Ag(111) leads to the formation of PbAg(2) surface alloy with a long range ordered (√3 × √3)R30° superstructure. A detailed analysis of this structure using low-energy electron diffraction (LEED) I-V measurements together with density functional theory (DFT) calculations is presented. We find strong correlation between experimental and calculated LEED I-V data, with the fit between the two data sets having a Pendrys reliability factor of 0.21. The Pb atom is found to replace one top layer Ag atom in each unit cell, forming a substitutional PbAg(2) surface alloy, as expected, with the Pb atoms residing approximately 0.4 Å above the Ag atoms due to their size difference. DFT calculations are in good agreement with the LEED results.

Dibromobianthryl ordering and polymerization on Ag(100)

We study the interaction between dibromobianthryl (DBBA) and the Ag(100) surface using scanning tunneling microscopy and density functional theory. DBBA is prochiral on adsorption and forms racemic domains with molecular rows aligned with the substrate nearest-neighbor [011] and [01¯1] directions. Deposition at elevated temperatures leads to the formation of disordered meandering graphene nanowires of constant width.