Spot Profile Analysis Low Energy Electron Diffraction Research Articles

Degeneracy in Intercalated Pb Phases under Buffer-Layer Graphene on SiC(0001) and Diffuse Moiré Spots in Surface Diffraction.

First-principles density functional theory (DFT) is used to analyze the stability of Pb intercalated phases under buffer layer graphene on SiC(0001) as a function of the supercell size, Pb coverage, and degree of Pb ordering. By comparing the chemical potentials of such two-dimensional Pb structures, we find that there is a family of structurally distinct thermodynamically preferred Pb subsurface configurations with minute stability differences. These differences are comparable to the thermal energies at about 450 °C, where the Pb intercalated phases are grown. High-resolution surface-diffraction experiments using Spot Profile Analysis Low-Energy Electron Diffraction (SPA-LEED) confirm this high degree of degeneracy of the Pb intercalated phases from broad, low-intensity moiré spots observed exclusively from intercalated Pb. The low intensity of the moiré spots implies the coexistence of structurally different subsurface Pb phases.

Increasing the scan speed in high resolution, low energy electron diffraction measurements by presetting the gate time.

We report on a speed-up data acquisition routine for recording intensities in reciprocal space (k-space) with increased scan speed by a single point detector. It is designed for recording low energy electron diffraction (LEED) data with high resolution by a spot profile analysis LEED instrument. It counteracts the problem of long acquisition times that are encountered when larger areas in the reciprocal space are scanned. It exploits the fact that in typical LEED images of ordered surfaces, more than 90% of the data points in k-space belong to the low-intense background, which is often not of interest. Only about 10% of the data points are related to the relevant diffraction features, namely, the LEED spots. Often it is not necessary to measure the background with the same statistical significance as measuring those points that contain information. The data points belonging to the LEED spots can be discriminated from those of the background by their higher intensities. An acquisition routine that sets an increased gate time for the counting in response to higher intensities thus safeguards good statistics for data points of the LEED spots and saves measurement time when recording data points of the background with small gate times. For typical LEED images, a reduction of the total acquisition time by a factor of about 10 is obtained. We give examples of one- and two-dimensional scans from current experiments, recorded with and without the speed-up routine. We further discuss how the routine supports the measurement of energy dependent reciprocal space maps.

Sn intercalation into the BL/SiC(0001) interface: A detailed SPA-LEED investigation

Growth of epitaxial graphene (EG) with desired properties and formation of new 2D interfaces can be achieved by intercalation of new elements into the carbon buffer layer (BL)/SiC(0001) interface. In this study, we investigated the formation of various ordered Sn-interface structures and, associated with it, the formation of quasi-free monolayer graphene by means of high-resolution spot profile analyzing low energy electron diffraction (SPA-LEED). The analyses of the diffraction patterns and the diffraction spot intensities allowed us to identify various long-range ordered interface structures as a function of the annealing temperature, e.g. (1 × 1), (3×3)R30° and (39×39)R16.1°. The ordering process at the interface and accompanying onset of deintercalation was controlled and monitored by high angular resolution and energy dependent measurements. Besides, for Sn sub-monolayer intercalation coverages, also a (3×3)R30° reconstruction with respect to EG was found, which indicates a broken Kekulé structure of the π-electrons in EG.

Boron nitride on SiC(0001)

The promising properties of heterostructures of 2D materials call for scalable sample production via epitaxy. The authors focus on surface structures obtained in a surfactant atmosphere in which a boron nitride template layer forms on SiC(0001). Remarkably, they find that this template is a hexagonal B${}_{x}$N${}_{y}$ layer, but not high-quality hBN. Experiments with the normal-incidence x-ray standing wave technique and spot-profile analysis low-energy electron diffraction reveal the $R{0}^{\ensuremath{\circ}}$ orientation of the layer, the presence of an unexpected boron buffer layer, and the interlayer distances with sub-Angstrom precision.

Adsorption of S on Si(111) with M4 × 4 superstructure

The atomic and electronic structures are calculated for the M4 × 4 superstructure of S/Si(111), which was recently identified by Schmidt et al. [Surf. Sci.694 (2020) 121561] by using the spot profile analysis low-energy electron diffraction (SPALEED) and confirmed by scanning tunneling microscopy (STM). The electronic band structures are found to be semiconducting in nature for three different S structures: monomer, Dimer-A and Dimer-B, each of which saturates all the Si dangling bonds. Due to the varying numbers of S atoms per unit cell, we have calculated the lowest energy phase in the accessible S chemical potential range. Dimer-A and Dimer-B are the lower energy phase and their accessible chemical potential value is less than the monomer case, in excellent agreement with the results of Schmidt et al. Dimer-B is slightly more stable geometry than Dimer-A. Application of the nudged elastic band (NEB) method suggests that there is a rotational activation barrier of 40 meV along the Dimer-A–Dimer-B reaction path.

Adsorbate induced manipulation of 1D atomic wires: Degradation of long-range order in the Si(553)-Au system

Deposition of Au on vicinal Si(553) surfaces results in the self-assembly of one-dimensional (1D) Au atomic wires. Charge transfer from the Au wire to the Si step edge leads to a chain of Si dangling-bond orbitals with a long range ordered threefold periodicity along the steps and finite interchain interaction perpendicular to the steps. Employing spot-profile analysis low-energy electron diffraction (SPA-LEED) we observed a broadening of spot width with time, indicative for the degradation of Si dangling-bond chain and Au wire length. We introduce a new mechanism how adsorbates act as origin for this degradation beyond the intuitive picture of bond saturation. Here, zero-dimensional anti-phase translational domain boundaries are generated which immediately destroy the long-range order along and perpendicular to the steps, respectively. From the temporal evolution of the decreasing coherence length, we conclude that the Au wires are less reactive to adsorption than the Si dangling bond chains.

Adsorption of sulfur on Si(111)

The adsorption of S on Si(111)- 7 × 7 has been investigated for different preparation schemes and parameters. S was supplied from an electrochemical Ag2S cell. For room temperature adsorption and subsequent annealing, no ordered S induced reconstruction can be observed with spot profile analysis low-energy electron diffraction (SPALEED). S deposition at temperatures above about 400 ∘C, however, leads to a well-ordered reconstruction. Judging from the LEED pattern, the same reconstruction was already observed by Metzner et al. [Surf. Sci. 377–379 (1997) 71–74] who identified it as 4 × 4 reconstruction. The upper temperature limit for the preparation of this superstructure depends on S flux, which is needed to compensate for desorption. Prolonged S exposure leads to surface roughening, as observed with SPALEED and scanning tunneling microscopy (STM), pointing to surface etching by S. From our SPALEED data, we can conclude that the observed reconstruction is not a 4 × 4 reconstruction, but a (2012) superstructure with a rectangular unit cell that exists in three rotational domains, as confirmed by STM. Different structural trial models have been assessed with density functional theory. Among these model structures, a configuration with dimers adsorbed on bridging sites, with a S coverage of 1 monolayer, is most likely, since it is energetically favorable and is in agreement with all experimental results.

Growth-mode investigation of epitaxial EuS on InAs(100)

A persistent challenge in the field of spintronics is the search for suitable materials that enable the circumvention of the impedance mismatch preventing efficient spin-injection from metallic ferromagnetic conductors into semiconductors. One promising material is europium sulfide (EuS), a ferromagnetic semiconductor below the Curie temperature of 16.5 K. Investigation and optimization of the conditions required for high-quality growth of epitaxial EuS films on suitable substrates are thus of particular interest for the creation of efficient devices. We present the results of a growth-mode study employing atomic force microscopy and spot-profile analysis low-energy electron diffraction (SPA-LEED) of epitaxial EuS thin films deposited by electron-beam evaporation on InAs(100) substrates with varying combinations of, respectively, growth and annealing temperatures, Tg and Ta, from room temperature to 400 °C. We observed Stranski-Krastanov-like growth featuring low-roughness surfaces with root mean square values between 0.4 – 0.9 nm for all temperature combinations. An increased tendency for nucleation into grains and islands was observed for higher Ta from 300 – 400 °C. The corresponding nucleation mode, defined by varying degrees of 2D and 3D nucleation, was dependent on Tg. A 2D island growth mode was observed for Tg = 150 °C and Ta = 400 °C featuring a sharp and bright SPA-LEED pattern. This suggests the formation of a highly ordered, smooth surface for these growth conditions thereby providing a good starting point for optimization attempts for potential future devices.

Growth of Epitaxial 3,4,9,10-Perylene Tetracarboxylic Dianhydride on Bi-Terminated Silicon

The epitaxial quality of thin films crucially depends on their interaction with the substrate. Up to now, Ag-terminated Si(111) has been employed as the model substrate for the growth of 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) on semiconductors. In this study, we will show that Bi termination results in PTCDA films of superior epitaxial quality. We have studied the growth of PTCDA on bismuth-passivated Si(111) in detail by means of spot profile analysis of low-energy electron diffraction (SPA-LEED), X-ray photoemission spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and scanning tunneling microscopy (STM). The XPS results reveal the presence of intact PTCDA molecules on the surface upon adsorption. NEXAFS data indicate the PTCDA molecules being oriented with their molecular plane parallel to the surface. STM shows a very smooth growth front of the PTCDA film, preserving the step structure of the substrate. High-resolution SPA-LEED data demonstrate the presence of a multidomain surface with a rich variety of PTCDA surface structures, which were identified to be most prominently herring-bone polytypes. However, in the monolayer range, quadratic brick-wall structures and a nearly square-like structure as well as a perylene-like structure have also been found. Despite the simultaneous presence of multiple domains, the individual domains show excellent lateral ordering, with larger domain sizes as compared to the case of Ag-terminated Si(111).

Thermal stability and interlayer exchange processes in heterolayers of TiOPc and PTCDA on Ag(1 1 1)

Organic–organic interfaces, in particular donor–acceptor type heterointerfaces, represent central elements of organic electronic devices. Understanding and controlling their physical properties is key to improve and modify their performance. For this purpose we have investigated the structural properties and thermal evolution of molecular heterointerface model systems. Specifically, various stacked titanyl-phthalocyanine (TiOPc)–3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) heterolayers grown on Ag(1 1 1) have been examined using Fourier transform infrared absorption spectroscopy and spot-profile analysis low-energy electron diffraction. An accurate description of the thermal evolution and prevalence of the various phases of TiOPc and PTCDA is derived from the spectral signatures of the two molecular species explored in previous studies. Exceptionally high thermal stability is found for stacked heterolayers comprising TiOPc double layers with characteristic up–down arrangement of its axial Ti–O unit and single layers of PTCDA. Thereby, interlayer exchange is negligible in a wide temperature range ( K). This is ascribed to attractive intermolecular interaction (dipole–dipole interaction, hydrogen bonding) among the TiOPc molecules oriented face-to-face within the TiOPc bilayer sheet. Stacked layers of comprising single layers of TiOPc and of PTCDA turn out to be thermally much less stable and more heterogeneous. In the course of their thermal evolution, a number of processes such as interlayer exchange, TiOPc double-layer formation and dewetting are encountered.

Growth of Ag(1 1 1) on Si(1 1 1) with nearly flat band and abrupt interface

Growth of Ag films of up to 30 nm thickness on Si(1 1 1) 7 × 7 at room temperature is investigated by low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). LEED revealed the coexistence of Ag and Si spots starting with 1 monolayer (ML) of Ag deposited. The Ag lattice constant, starting with 25 ML, is slightly higher than for bulk Ag and increase linearly with Ag thickness, reaching about 4.2 nm for the thickest films. The average terrace widths detected from LEED spot profile analysis are about 30 nm for clean Si(1 1 1) 7 × 7 and about 5.5 nm for the thickest Ag(1 1 1) film, in agreement with STM observations. The intensity variation of core levels analyzed by XPS is taken into account by a model assuming the initial formation of Ag islands with linear variation of coverage vs. the amount of Ag deposited, followed by growth in a quasi layer-by-layer mode. The interface barrier is in the range of 0.4 eV, lower than all values reported previously. Ag deposited on Si(1 1 1) 7 × 7 at room temperature provides flat Ag(1 1 1) for synthesis of 2D materials, and may be used for low barrier Schottky diodes.

Surface reconstruction of Pt(001) quantitatively revisited

The complex hexagonal reconstructions of the (001) surfaces of platinum and gold have been under debate for decades. Here, the structural details of the Pt(001) reconstruction have been quantitatively reinvestigated by combining the high resolving power of scanning tunneling microscopy (STM) and spot profile analysis low energy electron diffraction (SPA-LEED). In addition, LEED simulations based on a Moir\'e approach have been applied. Annealing temperatures around 850 \ifmmode^\circ\else\textdegree\fi{}C yield a superstructure that approaches a commensurable $c(26.6\phantom{\rule{0.16em}{0ex}}\ifmmode\times\else\texttimes\fi{}\phantom{\rule{0.16em}{0ex}}118)$ substrate registry. It evolves from a Moir\'e-like buckling of a compressed hexagonal top layer (hex) where atomic rows of the hex run parallel to atomic rows of the square substrate. Annealing at 920 \ifmmode^\circ\else\textdegree\fi{}C stimulates a continuous rotation of the hex where all angles between \ifmmode\pm\else\textpm\fi{}0.7\ifmmode^\circ\else\textdegree\fi{} are simultaneously realized. At temperatures around 1080 \ifmmode^\circ\else\textdegree\fi{}C, the nonrotated hex coexists with a hex that is rotated by about 0.75\ifmmode^\circ\else\textdegree\fi{}. Annealing at temperatures around 1120 \ifmmode^\circ\else\textdegree\fi{}C yield a locking of the hex in fixed rotation angles of 0.77\ifmmode^\circ\else\textdegree\fi{}, 0.88\ifmmode^\circ\else\textdegree\fi{}, and 0.94\ifmmode^\circ\else\textdegree\fi{}. At temperatures around 1170 \ifmmode^\circ\else\textdegree\fi{}C, the Pt(001)-hex-R 0.94\ifmmode^\circ\else\textdegree\fi{} prevails as the energetically most favored form of the rotated hex.

Isotropic thin PTCDA films on GaN(0 0 0 1)

The growth of 3, 4, 9, 10-perylene tetracarboxylic dianhydride (PTCDA) on the Ga-polar GaN(0 0 0 1) surface has been studied by x-ray photoelectron spectroscopy (XPS), spot profile analysis low-energy electron diffraction (SPA-LEED), near edge x-ray absorption fine structure (NEXAFS), and scanning tunneling microscopy (STM). The stoichiometric ratios derived from XPS indicate that the molecules remain intact upon adsorption on the surface. Furthermore, no chemical shifts can be observed in the C 1s and O 1s core levels with progressing deposition of PTCDA, suggesting none or only weak interactions between the molecules and the substrate. NEXAFS data indicate the PTCDA molecules being oriented with their molecular plane parallel to the surface. High-resolution STM shows PTCDA islands of irregular shape on the sub-micron scale, and together with corresponding SPA-LEED data reveals a lateral ordering of the molecules that is compatible with the presence of (1 0 2) oriented PTCDA nano-crystals. SPA-LEED moreover clearly shows the presence of homogeneously distributed rotational domains of two-dimensionally isotropic PTCDA.

Structural and Vibrational Properties of CuPc/Ag(111) Ultrathin Films

The initial stages of copper(II)–phthalocyanine (CuPc) thin film growth on Ag(111) have been investigated using Fourier transform infrared absorption spectroscopy (FT-IRAS), spot profile analysis low-energy electron diffraction (SPA-LEED), and thermal desorption spectroscopy (TDS). Starting at (sub)monolayer coverages up to 5 monolayers (ML), a number of ordered overlayers are found. Vibrational spectroscopy shows characteristic spectroscopic signatures for the individual submonolayer phases as well as for the bilayer, trilayer, and multilayers. Highly asymmetric line shapes of the in-plane vibrational modes of submonolayer CuPc provide unequivocal evidence for interfacial dynamical charge transfer between the metal electronic states and CuPc molecular orbitals, indicative for a partially filled LUMO at the Fermi energy as well as the prevalence of severe nonadiabaticity in the electron–vibron coupling. Growth of the second and third CuPc layers proceeds in a layer-by-layer fashion (Frank van der Merwe gr...

A combined STM and SPA-LEED study of the “explosive” nucleation and collective diffusion in Pb/Si(111)

A novel type of very fast nucleation was recently found in Pb/Si(111) with 4- to 7-layer high islands becoming crystalline in an “explosive” way, when the Pb deposited amount in the wetting layer is compressed to θc~1.22ML, well above the metallic Pb(111) density. This “explosive” nucleation is very different from classical nucleation when island growth is more gradual and islands grow in size by single adatom aggregation [8]. In order to identify the key parameters that control the nucleation we used scanning tunneling microscopy (STM) and spot profile analysis low energy electron diffraction (SPA-LEED). It was found that the number and duration of steps in iterative deposition used to approach θc and the flux rate have dramatic effects on the crystallization process. Larger depositions over shorter times induce greater spatial coverage fluctuations, so local areas can reach the critical coverage θc easier. This can trigger the collective motion of the wetting layer from far away to build the Pb islands “explosively”. The SPA-LEED experiments show that even low flux experiments in iterative deposition experiments can trigger transfer of material to the superstable 7-layer islands, as seen from the stronger satellite rings close to the (00) spot.

Growth of NaCl on thin epitaxial KCl films on Ag(100) studied by SPA-LEED

We investigated the growth of NaCl on thin (100)-oriented films of KCl by spot profile analysis of low energy electron diffraction (SPA-LEED). The underlying question of this investigation was how the system accommodates to the misfit of −10% between the NaCl and KCl lattices. The KCl films (3 atomic layers thick) were epitaxially grown on a Ag(100) single crystal. We studied the heteroepitaxial growth of NaCl on KCl at 300K and at 500K, respectively. At 300K, the first NaCl monolayer (ML) grows pseudomorphically on the KCl film. From the second layer onward, the NaCl lattice relaxes. The NaCl multilayers roughen, and a small rotational disorder (±4°) of the NaCl domains is observed. The roughening results from the formation of multilayer islands of limited lateral size due to the misfit to the pseudomorphic first NaCl layer. At a growth temperature of 500K, no pseudomorphic NaCl layer forms, instead relaxed multilayer island growth of NaCl is observed from the first layer onward. Similarly to the growth at 300K, we find NaCl multilayer islands of limited lateral size. For both temperatures, we explain this growth behavior by the misfit that makes the adsorption sites at the island edges of the first relaxed NaCl layer less favorable for larger islands, promoting nucleation of multilayer islands.

Pentacene/Cu(110) interface formation monitored byin situoptical spectroscopy

The adsorption of pentacene on the Cu(110) surface has been investigated by reflectance difference spectroscopy (RDS) and spot profile analysis low energy electron diffraction (SPA-LEED). The sensitivity of RDS to electronic transitions involving both surface states and intramolecular transitions allows a close monitoring of the formation of interfacial electronic states and structural phase transitions of the pentacene monolayer on Cu(110).

To tilt or not to tilt: Correction of the distortion caused by inclined sample surfaces in low-energy electron diffraction

Low-energy electron diffraction (LEED) is a widely employed technique for the structural characterization of crystalline surfaces and epitaxial adsorbates. For technical reasons the accessible reciprocal space is limited at a given primary electron energy E. This limitation may be overcome by sweeping E to observe higher diffraction orders decisively enhancing the quantitative examination. Yet, in many cases, such as molecular films with rather large unit cells, the adsorbate reflexes become less pronounced at energies high enough to observe substrate reflexes. One possibility to overcome this problem is an intentional inclination of the sample surface during the measurement at the expense of the quantitative interpretability of then severely distorted diffraction patterns. Here, we introduce a correction method for the axially symmetric distortion in LEED images of tilted samples. We provide experimental confirmation for micro-channel plate LEED and spot-profile analysis LEED instruments using the (7×7) reconstructed surface of a Si(111) single crystal as a reference sample. Finally, we demonstrate that the correction of this distortion considerably improves the quantitative analysis of diffraction patterns of adsorbates since substrate and adsorbate reflexes can be evaluated simultaneously. As an illustrative example we have chosen an epitaxial monolayer of 3,4,9,10-perylenetetracarboxylic dianhydride on Ag(111) that is known to form a commensurate superstructure.

Surface structure of Pd(111) with less than half a monolayer of Zn

We have characterized the structural properties of submonolayer amounts of Zn on Pd(111) using scanning tunneling microscopy (STM) and spot-profile analysis low energy electron diffraction (SPA-LEED). Following room temperature deposition of ≈0.06 monolayers (ML) Zn onto Pd(111), we observe the substitution of Zn for Pd in the surface layer. At ≈0.20 ML of deposited Zn, STM reveals a locally ordered phase with a (2/√3 × 2/√3)R30° unit cell located near Zn substitutions; SPA-LEED patterns reveal the same periodicity. We attribute this phase to the metastable bonding of atoms or clusters predominantly in hollow sites surrounding Zn substitutions in the surface layer. At ≈0.4 ML, STM images reveal local (√3 × √3)R30° and (2 × 1) ordering on surfaces annealed to 350 K. At coverages near 0.5 ML, both STM and SPA-LEED show the onset of the formation of the (2 × 1) ordering associated with the Zn : Pd 1 : 1 alloy phase. At all coverages, the surface is dominated by island growth; the islands' size and density is shown to depend critically on annealing at temperatures as low as 350 K. These results provide insight into the structural features of a Zn/Pd(111) coverage regime that has been much debated in recent years.

Determination and correction of distortions and systematic errors in low-energy electron diffraction

We developed and implemented an algorithm to determine and correct systematic distortions in low-energy electron diffraction (LEED) images. The procedure is in principle independent of the design of the apparatus (spherical or planar phosphorescent screen vs. channeltron detector) and is therefore applicable to all device variants, known as conventional LEED, micro-channel plate LEED, and spot profile analysis LEED. The essential prerequisite is a calibration image of a sample with a well-known structure and a suitably high number of diffraction spots, e.g., a Si(111)-7×7 reconstructed surface. The algorithm provides a formalism which can be used to rectify all further measurements generated with the same device. In detail, one needs to distinguish between radial and asymmetric distortion. Additionally, it is necessary to know the primary energy of the electrons precisely to derive accurate lattice constants. Often, there will be a deviation between the true kinetic energy and the value set in the LEED control. Here, we introduce a method to determine this energy error more accurately than in previous studies. Following the correction of the systematic errors, a relative accuracy of better than 1% can be achieved for the determination of the lattice parameters of unknown samples.