Low-energy Electron Diffraction Research Articles

Atomic surface control of Ge(100) in MOCVD reactors coated with (Ga)As residuals

Heteroepitaxy of planar, low-defect III-V semiconductor layers on Ge(100) requires a single-domain substrate surface, where dimer rows are aligned in parallel on atomically well-ordered terraces, which are separated by steps of even numbered atomic height. The presence of Ga and As in the sample ambience crucially impacts the preparation of such Ge(100) surfaces. Ga and As are commonly omnipresent, when applying metalorganic chemical vapor deposition (MOCVD), either directly supplied by precursors, in the form of MOCVD reactor residuals, or both. We study the impact of the growth conditions on the Ge(100) surface formation in situ, in dependence on the reactor pre-conditioning, the type of As supply, and/or temperature, utilizing surface-sensitive reflection anisotropy spectroscopy. We benchmark the in situ spectra to in system X-ray photoelectron spectroscopy, low energy electron diffraction and scanning tunneling microscopy. We find that interaction of tertiarybutylarsine (TBAs) with a coating of the inner MOCVD reactor walls by GaAs residuals favors desorption of As from reactor parts resulting in As-dimers on the Ge(100) surface, which are rotated by 90° compared to preparation routes employing TBAs in Ga-free ambience. The optical in situ control enables precise adjustment and switching between distinct Ge(100) surface reconstructions for subsequent III-V heteroepitaxy.

Non-conventional bell-shaped diffuse scattering in low-energy electron diffraction from high-quality epitaxial 2D-materials

A broad, bell-shaped intensity component is observed in low-energy electron diffraction from high-quality epitaxial 2D-systems. Three 2D-systems, graphene on Ir(111), graphene on SiC(0001), and hexagonal boron nitride on Ir(111), have been prepared in situ under ultra-high vacuum conditions. In all three systems—independent of substrate material—similar strong diffuse intensity is observed, exhibiting a width as large as 50% of the Brillouin zone and an integrated intensity more than 10 times the intensity of the Bragg spots. The presented experimental results provide evidence for a common origin of such diffuse diffraction intensity in different atomically thin 2D-materials.

Electronic properties of single-layer CoO2/Au(111)

We report direct measurements via angle-resolved photoemission spectroscopy (ARPES) of the electronic dispersion of single-layer (SL) CoO2. The Fermi contour consists of a large hole pocket centered at the point. To interpret the ARPES results, we use density functional theory (DFT) in combination with the multi-orbital Gutzwiller Approximation (DFT+GA), basing our calculations on crystalline structure parameters derived from x-ray photoelectron diffraction and low-energy electron diffraction. Our calculations are in good agreement with the measured dispersion. We conclude that the material is a moderately correlated metal. We also discuss substrate effects, and the influence of hydroxylation on the CoO2 SL electronic structure.

Nearly-grazing-incidence-high-temperature sputtering of Ruthenium(0001) surface

An atomically clean and ordered Ru(0001) surface with sharp low energy electron diffraction (LEED) spots, dispersing bands in angle-resolved photoemission spectroscopy, and the intensity-voltage (I-V) curves from LEED similar to the data existing in literature has been obtained by nearly-grazing-incidence-high-temperature sputtering at 973 K. This method of surface preparation is advantageous because it requires significantly lower temperature compared to 1800–1300 K used earlier, and also does not require any oxygen exposure. Both from the experiment as well as Monte Carlo calculations, the efficacy of the nearly-grazing incidence angle of sputtering (70°) is shown.

Combining low and high electron energy diffractions as a powerful tool for studying 2D materials

Two-dimensional (2D) materials are among the most studied ones nowadays, because of their unique properties. They are made of single- or few-atom-thick layers whose variation in the stacking sequence may result in a variety of crystallographic structures, whether they are assembled by van der Waals forces or covalently bonded. Although identifying both the number of layers and the stacking sequence is of an utmost importance because of the driving role these parameters have on the properties, there is currently no technique available to do so. We demonstrate here that combining low energy (1–10 keV) electron diffraction with the usual high energy (> 50 keV) electron diffraction on the same 2D object is able to fill the gap. We illustrate this by taking the examples of a variety of 2D materials, built from either a single type of atom with low Z-number such as graphene (C), or two types of atoms with low Z-number such as diamane (C2H), or two types of atoms with high Z-number such as MoS2. Meanwhile, we propose a simplified method for comparing calculated patterns to experimental ones, and discuss the limitation of the technique.

Ultrafast spot-profile LEED of a charge-density wave phase transition

We investigate the optically driven phase transition between two charge-density wave (CDW) states at the surface of tantalum disulfide (1T-TaS2). Specifically, we employ a recently improved ultrafast low-energy electron diffraction setup to study the transition from the nearly commensurate to the incommensurate (IC) CDW state. The experimental setup allows us to follow transient changes in the diffraction pattern with high momentum resolution and 1-ps electron pulse duration. In particular, we trace the diffraction intensities and spot profiles of the crystal lattice, including main and CDW superstructure peaks, as well as the diffuse background. Harnessing the enhanced data quality of the instrumental upgrade, we follow the laser-induced transient disorder in the system and perform a spot-profile analysis that yields a substantial IC-peak broadening for very short time scales followed by a prolonged spot narrowing.

A New Method for Evaluating Li-Ion Battery Anode Materials Based on Surface Compositional and Structural Characterization

There is a global effort to develop safer lithium-ion batteries (LIB) with a high energy density and long lifetime. Material properties, their mutual interactions, and active interfaces are key factors in battery performance. Popular methods involve the mixing of different ingredients and development of a suitable fabrication process. Significant effort has been spent to understand the reaction mechanism of battery materials, but this is very challenging due to high system complexity. Different techniques have been developed to follow these reactions, and most significantly, the reactions between Li and electrode materials. Our team has developed a new method to characterize Li thermal diffusion and structural interaction on the surfaces of potential anode and cathode materials. This method is based on surface crystallographic and compositional characterization of deposited ultra-thin film of Li on potential single crystal or polycrystalline anode material. Surface crystallography characterization is done with w Low Energy Electron Diffraction (LEED) and surface composition with Auger Electron Spectroscopy (AES). This characterization monitors Li thermal diffusion into the electrode surface at room temperature and changes in surface crystalline structure and composition. The data provides a strong link between Lithium thermal diffusion and lithiation processes in LIB. The dynamic interaction of Li is monitored at the nanoscale level and gives the direct response how Li atoms interact with the substrate. The diffusion of evaporated Li on single crystals of HOPG, Si(111)-(211)-(100), SiC-6H, CVD-Diamond and LiNbO3 have been performed. The results shows that HOPG is the excellent reference substrate for this method as Li diffuses at room temperature and surface crystallography of HOPG remains unchanged. The structural reaction of Li with Si is very strong causing LEED pattern to disappear and there is no Li diffusion at room temperature as indicated from AES data. The data for SiC-6H and LiNbO3 shows better Li diffusional behavior than on Si but not as good as on HOPG. This method of using a single crystal substrate and basic surface characterization techniques is providing simple nanoscale access into the chemical reactions between Li and the substrate material that will result in better understanding of Lithium diffusion in the fabricated battery electrodes. The initial material classification for “native” Lithium thermal diffusion properties is proposed.

Surface and interface analysis of a low-dimensional Au–Si surface alloy on Au(110) by means of XPS and XPD

The chemical and structural characteristics of a low-dimensional Au–Si surface alloy are presented in this work. Alloy formation was obtained by deposition of a sub-monolayer Si on Au(110). This preliminary phase to Si nano-ribbons is being investigated, as the transition from clean Au(110) to a silicon nano-ribbon coated surface is not yet understood. A multiple technique study has been carried out for detailed atomic structure determination and chemical investigation. Particular attention is paid to the clarification of the structural arrangement at the surface and at the interface. Using low-energy electron diffraction, the periodicity of the structure on long-range order could be examined. By means of high-precision photoemission measurements using synchrotron radiation, the electronic and atomic structure of the alloy can be presented. The investigation by photoelectron spectroscopy (XPS) using soft x-rays for a high surface sensitivity showed different chemical environments in the high-resolution spectra. The x-ray photoelectron diffraction (XPD) measurements, which are sensitive to the local atomic order, gave an approach to the structural configuration of the alloy. A new structural arrangement was found simulating both Au and Si XPD patterns. The results are compared to former proposed structure models. A deconvolution of the Si 2p XPD pattern revealed the origin of two chemically shifted XPS components.

Atomic and electronic structures of Si/Ge(100) interfaces studied by high-resolution photoelectron spectroscopy and scanning tunneling microscopy

The close similarity of silicon and germanium, isoelectronic group-IV elements, makes the integration of Ge layers on Si substrates suitable for technology development, but the atomic and electronic structures of ${\mathrm{Si}}_{1\ensuremath{-}x}{\mathrm{Ge}}_{x}$ surfaces are still an open issue, in particular, for the alloy systems where Si is deposited on the Ge substrate. In this study, utilizing low-energy electron diffraction, scanning tunneling microscopy, and photoelectron spectroscopy using synchrotron radiation, we demonstrate that the formation mechanisms of the Si-on-Ge structures are controlled by two interface phenomena, namely Si indiffusion and Ge segregation on top of this surface. Employing these phenomena and controlling the Si quantity, one can synthesize the well-defined crystalline Ge-(2 \ifmmode\times\else\texttimes\fi{} 1)/${\mathrm{Si}}_{1\ensuremath{-}x}{\mathrm{Ge}}_{x}$/Ge(100) stacks where the number of Si atoms at the host Ge lattice sites can be tuned. Using the obtained data on the atomic and electronic structures of such systems, we also propose a method for interface engineering of Ge/Si/Ge stacks with tailored properties as promising templates for growing the device junctions.

Ni-modified Fe3O4(001) surface as a simple model system for understanding the oxygen evolution reaction

Electrochemical water splitting is an environmentally friendly technology to store renewable energy in the form of chemical fuels. Among the earth-abundant first-row transition metal-based catalysts, mixed Ni-Fe oxides have shown promising performance for effective and low-cost catalysis of the oxygen evolution reaction (OER) in alkaline media, but the synergistic roles of Fe and Ni cations in the OER mechanism remain unclear. In this work, we report how addition of Ni changes the reactivity of a model iron oxide catalyst, based on Ni deposited on and incorporated in a magnetite Fe3O4(001) single crystal, using a combination of surface science techniques in ultra-high vacuum such as low energy electron diffraction (LEED), x-ray photoelectron spectroscopy (XPS), low-energy ion scattering (LEIS), and scanning tunneling microscopy (STM), as well as atomic force microscopy (AFM) in air, and electrochemical methods such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in alkaline media. A significant improvement in the OER activity is observed when the top surface presents an iron fraction among the cations in the range of 20-40%, which is in good agreement with what has been observed for powder catalysts. Furthermore, a decrease in the OER overpotential is observed following surface aging in electrolyte for three days. At higher Ni load, AFM shows the growth of a new phase attributed to an (oxy)-hydroxide phase which, according to CV measurements, does not seem to correlate with the surface activity towards OER. EIS suggests that the OER precursor species observed on the clean and Ni-modified surfaces are similar and Fe-centered, but form at lower overpotentials when the surface Fe:Ni ratio is optimized. We propose that the well-defined Fe3O4(001) surface can serve as a model system for understanding the OER mechanism and establishing the structure-reactivity relation on mixed Fe-Ni oxides.

In-plane strain-free stanene on a Pd2Sn(111) surface alloy

Here we report the growth of laterally strain-free stanene, that is a two-dimensional (2D) honeycomb structure of tin atoms, on a Pd(111) crystal terminated by a ${\mathrm{Pd}}_{2}\mathrm{Sn}$ surface alloy. The atomic geometry and the electronic structure have been thoroughly investigated by scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), Auger electron spectroscopy, high-resolution synchrotron radiation photoemission spectroscopy, and advanced first principles calculations. The STM images clearly reveal the epitaxial growth of honeycomb stanene on the preformed ${\mathrm{Pd}}_{2}\mathrm{Sn}$ surface alloy. LEED patterns clearly show commensurate (\ensuremath{\surd}3\ifmmode\times\else\texttimes\fi{}\ensuremath{\surd}3)R30\ifmmode^\circ\else\textdegree\fi{} spots, corresponding to a lattice constant of 0.47 nm, in perfect accord with the cell size of free-standing stanene. The measured very low buckling, within 20 pm, is derived from section profiles of atomic-scale STM images. This contrasts the significantly larger buckling of free-standing stanene, possibly due to a STM tip effect as well as a non-negligible interaction with the underlying surface alloy. The electronic structure exhibits a characteristic 2D band with parabolic dispersion, which is in good accordance with electronic structure calculations in density functional theory.

High anisotropic inserted dendritic growth during first stage of Zn monolayer deposition on Ag(111) substrate

Sub-monolayer physical layer deposition of Zn on Ag(111) substrate at room temperature is investigated using Auger electron spectroscopy, low energy electron diffraction and scanning tunneling microscopy. We identified an original Zn highly-anisotropic structure in the shape of finger-like inserted dendrite in front of Zn monolayer growth. On the basis of STM observations, a mechanism of inserted dendritic growth and a mechanism of its transition to layered growth are proposed.

Growth of Ba–O ultrathin films on Pt(1 1 1) followed by Ti incorporation to prepare oxide crystalline approximants and quasicrystals

In this study, three different precursor Ba–O films on Pt(111) are characterized and the oxide crystalline approximant (OCA) and oxide quasicrystal (OQC) films are prepared by annealing after Ti deposition on the films. The prepared Ba–O ultra-thin films are BaO(100)–(√2×√2)R3°:Pt(111), Ba–O:Pt(111)–(2 × 2) and Ba–O:Pt(111)–(√13×√13)R13.9°, as determined using scanning tunneling microscopy, low-energy electron diffraction, and X-ray photoelectron spectroscopy. The phase transformation from an OCA film to an OQC film likely follows the mechanism where Ti is reduced and its surface atomic density decreased, while Ba is oxidized. The schematic structural models of the OCA film as Ba4Ti4O10 and the OQC film as Ba12Ti5O12, where the Ba atoms form a cluster tiling, are proposed.

Ce=O Terminated CeO2.

Multiply bonded lanthanide oxo groups are rare in coordination compounds and have not previously been reported for a surface termination of a lanthanide oxide. Here we report the observation of a Ce=O terminated ceria surface in a CeO2(111)‐(3 ×3 )R30° reconstruction of ≈3 nm thick ceria islands prepared on Pt(111). This is evidenced by scanning tunnelling microscopy (STM), low energy electron diffraction (LEED) and high‐resolution electron energy loss spectroscopy (HREELS) measurements in conjunction with density functional theory (DFT) calculations. A Ce=O stretching frequency of 775 cm−1 is observed in HREELS, compared with 766 cm−1 calculated by DFT. The calculations also predict that the Ce=O bond is weak, with an oxygen vacancy formation energy of 0.85 eV. This could play an important role in the facile removal of lattice oxygen from CeO2, accompanied by the reduction of CeIV to CeIII, which is a key attribute of ceria‐based systems in connection with their unique catalytic properties.

Ce=O Terminated CeO2

AbstractMultiply bonded lanthanide oxo groups are rare in coordination compounds and have not previously been reported for a surface termination of a lanthanide oxide. Here we report the observation of a Ce=O terminated ceria surface in a CeO2(111)‐( × )R30° reconstruction of ≈3 nm thick ceria islands prepared on Pt(111). This is evidenced by scanning tunnelling microscopy (STM), low energy electron diffraction (LEED) and high‐resolution electron energy loss spectroscopy (HREELS) measurements in conjunction with density functional theory (DFT) calculations. A Ce=O stretching frequency of 775 cm−1 is observed in HREELS, compared with 766 cm−1 calculated by DFT. The calculations also predict that the Ce=O bond is weak, with an oxygen vacancy formation energy of 0.85 eV. This could play an important role in the facile removal of lattice oxygen from CeO2, accompanied by the reduction of CeIV to CeIII, which is a key attribute of ceria‐based systems in connection with their unique catalytic properties.

Formaldehyde Selectivity in Methanol Partial Oxidation on Silver: Effect of Reactive Oxygen Species, Surface Reconstruction, and Stability of Intermediates

Selective oxidation reactions on heterogeneous silver catalysts are essential for the mass production of numerous industrial commodity chemicals. However, the nature of active oxygen species in such reactions is still debated. To shed light on the role of different oxygen species, we studied the methanol oxidation reaction on Ag(111) single-crystal model catalyst surfaces containing two dissimilar types of oxygen (electrophilic, Oe and nucleophilic, On). X-ray photoelectron spectroscopy and low energy electron diffraction experiments suggested that the atomic structure of the Ag(111) surface remained mostly unchanged after accumulating low Oe coverage at 140 K. Temperature-programmed reaction spectroscopic investigation of low coverages of Oe on Ag(111) revealed that Oe was active for methanol oxidation on Ag(111) with a high selectivity toward formaldehyde (CH2O) production. High surface oxygen coverages, on the other hand, triggered a reconstruction of the Ag(111) surface, yielding Ag oxide domains, which catalyzes methanol total oxidation to CO2 and decreases the formaldehyde selectivity. This important finding indicates a trade-off between CH2O selectivity and methanol conversion, where 93% CH2O selectivity can be achieved for an oxygen surface coverage of θO = 0.08 ML (ML = monolayer) with moderate methanol conversion, while methanol conversion could be boosted by a factor of ∼4 for θO = 0.26 ML with a suppression of CH2O selectivity to 50%. Infrared reflection absorption spectroscopy results and density functional theory calculations indicated that Ag oxide contains dissimilar adsorption sites for methoxy intermediates, which are also energetically less stable than that of the unreconstructed Ag(111). The current findings provide important molecular-level insights regarding the surface structure of the oxidized Ag(111) model catalyst directly governing the competition between different reaction pathways in methanol oxidation reaction, ultimately dictating the reactant conversion and product selectivity.

Absence of ferromagnetism in MnBi2Te4/Bi2Te3 down to 6 K

We successfully fabricated a ${\mathrm{MnBi}}_{2}{\mathrm{Te}}_{4}/{\mathrm{Bi}}_{2}{\mathrm{Te}}_{3}$ heterostructure by incorporating Mn and Te inside the topmost quintuple layer of ${\mathrm{Bi}}_{2}{\mathrm{Te}}_{3}$, as unambiguously confirmed by low-energy electron diffraction $I\text{\ensuremath{-}}V$ and scanning transmission electron microscopy measurements. The surface-state Dirac cone of the heterostructure showed little change compared to that of pristine ${\mathrm{Bi}}_{2}{\mathrm{Te}}_{3}$, and x-ray magnetic circular dichroism measurements showed that the system was paramagnetic down to 5.6 K. These results are in contrast to previous works on related materials that showed magnetic order around 10 K as well as theoretical predictions and suggest the intricacy of the magnetic properties of two-dimensional van der Waals magnets.

Highly Biaxially Strained Silicene on Au(111).

Many of graphene’s remarkable properties arise from its linear dispersion of the electronic states, forming a Dirac cone at the K points of the Brillouin zone. Silicene, the 2D allotrope of silicon, is also predicted to show a similar electronic band structure, with the addition of a tunable bandgap, induced by spin–orbit coupling. Because of these outstanding electronic properties, silicene is considered as a promising building block for next-generation electronic devices. Recently, it has been shown that silicene grown on Au(111) still possesses a Dirac cone, despite the interaction with the substrate. Here, to fully characterize the structure of this 2D material, we investigate the vibrational spectrum of a monolayer silicene grown on Au(111) by polarized Raman spectroscopy. To enable a detailed ex situ investigation, we passivated the silicene on Au(111) by encapsulating it under few layers hBN or graphene flakes. The observed spectrum is characterized by vibrational modes that are strongly red-shifted with respect to the ones expected for freestanding silicene. By comparing low-energy electron diffraction (LEED) patterns and Raman results with first-principles calculations, we show that the vibrational modes indicate a highly (>7%) biaxially strained silicene phase.

Ab Initio Theory of Photoemission from Graphene.

Angle-resolved photoemission from monolayer and bilayer graphene is studied based on an ab initio one-step theory. The outgoing photoelectron is represented by the time-reversed low energy electron diffraction (LEED) state , which is calculated using a scattering theory formulated in terms of augmented plane waves. A strong enhancement of the emission intensity is found to occur around the scattering resonances. The effect of the photoelectron scattering by the underlying substrate on the polarization dependence of the photocurrent is discussed. The constant initial state spectra are compared to electron transmission spectra of graphene, and the spatial structure of the outgoing waves is analyzed. It turns out that the emission intensity variations do not correlate with the structure of the spectra and are caused by rather subtle interference effects. Earlier experimental observations of the photon energy and polarization dependence of the emission intensity are well reproduced within the dipole approximation, and the Kohn–Sham eigenstates are found to provide a quite reasonable description of the photoemission final states.

Plasmon localization by adatoms in gold atomic wires on Si(775)

Self-organized gold chains on vicinal Si(111) surfaces represent prototype examples of quasi-one-dimensional objects that are stabilized by hybridization with Si surface states. Their plasmons contain important information about the unoccupied bandstructure close to the Fermi level. Using Si(775)–Au as an example, we report here the modifications of the plasmon dispersion by the simple atomic adatom species H and O. Using a combination of low energy electron diffraction and high-resolution electron energy loss spectroscopy, we study the interconnection between plasmonic excitation and the corresponding local surface structure. Both adsorbates do not destroy metallicity, but, similar to Si(553)–Au, atomic hydrogen enhances dimerization of the Au chains, which at small concentrations counteracts the disorder introduced by random adsorption. This effect, most likely caused by electron donation of H to the surface states, is missing in case of adsorbed oxygen, so that only the effect of disorder is observed. For both adsorbates increasing disorder as a function of adsorbate concentration finally results in plasmon localization and opening of a band gap.