Low-energy Electron Diffraction Research Articles

Surface structure of MOVPE-prepared As-modified Si(100) substrates

In the pursuit of high-efficiency tandem devices for solar energy conversion based on III-V-semiconductors, low-defect III-V nucleation on Si(100) substrates is essential. Here, hydrogen and arsenic are key ingredients in all growth processes with respect to industrially scalable metalorganic vapor phase epitaxy. Our study provides insight into Si(100) surface preparation for the initial stage of III-V nucleation. The samples investigated, prepared on substrates with different offcut angles, show single domain surfaces consisting of rows of preferentially buckled dimers. Low energy electron diffraction and reflection anisotropy spectroscopy confirm well-defined (1 × 2)/(2 × 1) majority domains. Fourier-transform infrared spectroscopy revealed hydrogen bonding to the surface dimers, while no impurities were found by XPS. Density functional theory calculations support the experimental results and reveal a novel surface motif of H-passivated Si-As mixed dimers.

Influencing the surface quality of free-standing wurtzite gallium nitride in ultra-high vacuum: Stoichiometry control by ammonia and bromine adsorption

Gallium nitride (GaN), a wide bandgap semiconductor with absorption and emission in the ultraviolet/visible range, is proposed as an alternative to metallic surfaces for assembling organic molecular structures aiming at optoelectronic applications. However, the formation of a persistent surface oxide layer in air considerably limits the use of GaN for well-defined interfaces. In this work, we have investigated, characterized and processed n-type free-standing c-plane hexagonal wurtzite GaN crystals grown by hydride vapor phase epitaxy and ammonothermal growth methods. Surface cleaning and full removal of the oxide layer on GaN surfaces could be reproducibly achieved via sputtering and annealing cycles, as evidenced by X-ray photoelectron spectroscopy and low-energy electron diffraction. Scanning tunneling microscopy, however, indicated substantial roughening of the GaN surface and the formation of unwanted Ga-rich islands and clusters. Although ammonia (NH3) and bromine (Br) treatments compensated the N/Ga atoms ratio reduced by sputtering, the surface morphology remained rough, exhibiting randomly shaped and distributed hillocks. In addition, we studied the effect of electron bombardment on the surface quality of GaN during NH3 annealing, on-surface debromination and polymerization of 1,3,5-Tris(4-bromophenyl) benzene on GaN and removal of Ga atoms by Br atoms during the desorption.

Quasi-1D Moiré superlattices in self-twisted two-allotropic antimonene heterostructures.

Two-dimensional heterostructures, characterized by a twist angle between individual sublayers, offer unique and tunable properties distinct from standalone layers. These structures typically introduce a realm of exotic quantum phenomena due to the appearance of new, long range periodicities associated with Moiré superlattices. Using molecular beam epitaxy, we demonstrate the growth of bi-allotropic 2D-Sb heterostructures on a W(110) substrate composed of twisted α (α-Sb) and β (β-Sb) phases of antimonene. Due to the relatively weak interaction between sublayers, the twist angle is intrinsically determined for each heterostructure, revealing its inherent self-twisted nature. The different atomic lattice symmetries of both allotropes lead to the formation of distinctive quasi-1D Moiré superlattices, while the random nature of the twist angle allows for a wide modulation of the Moiré potential landscape. The observed Moiré patterns on β-Sb/α-Sb heterostructures were compared with a simple model, revealing satisfactory agreement with the experiments and strongly validating the formation of self-twisted β-Sb/α-Sb heterostructures. The samples were characterized in situ using low energy electron microscopy and diffraction techniques providing a real-time tracking of the growth process and insight into the atomic structure of the synthesized nanostructures.

Intrinsically Patterned Two-Dimensional Transition Metal Halides.

Patterning and defect engineering are key methods for tuning the properties and enabling distinctive functionalities in two-dimensional (2D) materials. However, generating 2D periodic patterns of point defects in 2D materials, such as vacancy lattices that can serve as antidot lattices, has been elusive until now. Herein, we report on 2D transition metal dihalides epitaxially grown on metal surfaces featuring periodically assembled halogen vacancies that result in alternating coordination of the transition metal atom. Using low-temperature scanning probe microscopy and low-energy electron diffraction, we identified the structural properties of intrinsically patterned FeBr2 and CoBr2 monolayers grown epitaxially on Au(111). Density functional theory reveals that Br vacancies are facilitated by low formation energies, and the formation of a vacancy lattice results in a substantial decrease in the lattice mismatch with the underlying Au(111). We demonstrate that interfacial strain engineering presents a versatile strategy for controlled patterning in two dimensions with atomic precision over several hundred nanometers to solve a long-standing challenge of growing atomically precise antidot lattices. In particular, patterning of 2D materials containing transition metals provides a versatile method to achieve unconventional spin textures with noncollinear spin.

Structure Determination of F4TCNQ on Ag(111): A Systematic Trend in Metal Adatom Incorporation.

A structure determination of the commensurate phase formed by 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (F4TCNQ) absorbed on Ag(111) is reported. Initial characterization was performed using low-energy electron diffraction and synchrotron radiation photoelectron spectroscopy, with quantitative structural data being provided by normal incident X-ray standing waves (NIXSW) and surface X-ray diffraction (SXRD). NIXSW data show the F4TCNQ molecule to adopt a "twisted" conformation on the surface, previously found to be associated with metal adatom incorporation into a 2d-metal-organic framework for F4TCNQ on Au(111), Ag(100), and Cu(111). SXRD results provide direct evidence of the presence of Ag adatoms that are found to occupy near-bridge or fcc hollow sites with respect to the underlying surface, at an adsorption height of 2.69 ± 0.10 Å. The results show a consistent pattern of behavior for F4TCNQ adsorption on the (111) surfaces of Cu, Ag, and Au.

In situ Low-Energy Electron Microscopy of Chemical Waves on a Composite V-oxide/Rh(110) Surface.

Chemical wave patterns and V-oxide redistribution in catalytic methanol oxidation on a VOx/Rh(110) surface have been investigated in the 10-4 mbar range with low-energy electron microscopy (LEEM) and micro spot low-energy electron diffraction (micro-LEED) as in situ methods. V coverages of θV=0.2 and 0.4 MLE (monolayer equivalents) were studied. Pulses display a c(2×2) pattern in the reduced part and (1×2) and c(2×8) structures in the oxidized part of the surface. At θV=0.4 MLE (1×2)/(1×4) patterns with streaks along the [001]-direction at the 1/8 positions are present on the oxidized part of the surface. This phase can be assigned to V-oxide. On a tentative basis, an excitation mechanism for pulses is presented, Annealing the surface to 990 K under reaction conditions results in a macroscopic hole pattern in which holes of low VOx coverage are surrounded by a V-oxide layer. Chemical waves propagate inside the holes as well as on the VOx covered parts of the surface. The results demonstrate for the first time that also in supported oxidic overlayers selforganization processes can take place leading to chemical waves and a large scale redistribution of the oxide.

Design, development, and performance of a versatile graphene epitaxy system for the growth of epitaxial graphene on SiC.

A versatile graphene epitaxy (GrapE) furnace has been designed and fabricated for the growth of epitaxial graphene (EG) on silicon carbide (SiC) in diverse growth environments ranging from high vacuum to atmospheric argon pressure. Radio-frequency induction enables heating capabilities up to 2000 °C, with controlled heating ramp rates achievable up to 200 °C/s. The details of critical design aspects and temperature characteristics of the GrapE system are discussed. The GrapE system, being automated, has enabled the growth of high-quality EG monolayers and turbostratic EG on SiC using diverse methodologies, such as confinement-controlled sublimation (CCS), open configuration, polymer-assisted CCS, and rapid thermal annealing. This showcases the versatility of the GrapE system in EG growth. Comprehensive characterizations involving atomic force microscopy, Raman spectroscopy, and low-energy electron diffraction techniques were employed to validate the quality of the produced EG.

Directional growth of iron oxide nanowires on a vicinal copper surface

Single-crystal magnetic nanostructures with well-defined shapes attract lots of interest due to their potential applications in magnetic and spintronic devices. However, development of methods allowing controlling their mutual crystallographic and geometric orientation constitutes a significant scientific challenge. One of the routes for obtaining such structures is to grow the materials epitaxially on naturally-structured supports, such as vicinal surfaces of single-crystal substrates. Iron oxides are among the most well-known magnetic materials which, depending on the phase, may exhibit ferro/ferri- or antiferromagnetic ordering. We have grown iron oxide nanowires on a Cu(410) single-crystal substrate faceted with molecular oxygen. Scanning tunneling microscopy and low energy electron diffraction revealed that the oxide grows in the [111] direction, along the step edges of the substrate and rotated by ±15° with respect to the [010] direction of copper atomic terraces (so that the the growing elongated structures are orientated parallel to each other). Notably, x-ray photoelectron spectroscopy confirmed that the nanowires represent the ferrimagnetic γ-Fe2O3 (maghemite) iron oxide phase, while micromagnetic simulations indicated that the wires are single-domain, with the easy magnetization axis orientated in-plane and along the long axis of the wire.

Synthesis and characterisation of Cu2Ge, a new two-dimensional Dirac nodal line semimetal

Dirac nodal line (DNL) semimetals are a novel class of topological materials in which the valence and conduction bands touch along lines in the reciprocal space, with linear dispersion. These materials attract a growing attention, but the experimental realizations for two-dimensional systems are sparse. This article reports the first experimental realization of a two-dimensional hexagonal monolayer Cu2Ge, grown by evaporation of Ge on a Cu(111) substrate. Through a combination of low-energy electron diffraction XPS and ARPES measurements, it is shown that the surface presents all characteristics expected from calculations for a free-standing Cu2Ge monolayer. More specifically, the preservation of the two concentric nodal lines around the Γ point indicates weak interactions between the Cu2Ge surface and its Cu(111) substrate, making it an ideal system for the study of DNL materials.

Epitaxial Fe/Rh bilayers for efficient spin-to-charge conversion

To address the spin pumping in the conventional ferromagnetic/“normal” metal systems, we fabricated 6 nm Fe/1–15 nm Rh epitaxial bilayers and determined the g-factor, magnetic anisotropy, and magnetization damping by combining both 0–40 GHz CPW-based frequency-dependent and cavity-based 9.56 GHz in-plane angular-dependent ferromagnetic resonance measurements at room temperature. Auger electron spectroscopy and low-energy electron diffraction show that Rh grows epitaxially on Fe. The epitaxial bilayers exhibit a high spin mixing conductance gmix↑↓=(2.9±0.2)×1019 m−2 and a spin diffusion length in Rhodium λsd=9.0±1.3 nm. This makes Rh comparable to Pt and Pd in terms of spin pumping and spin transport efficiency at room temperature.

Tellurization of Pd(111) revisited: Formation of a TePd[formula omitted] surface alloy but no PdTe[formula omitted] monolayer

In a recent publication [2D Materials, 8, 045033 (2021)], it was reported that the growth of a monolayer PdTe2 in ultra-high vacuum could be achieved by deposition of tellurium on a palladium (111) crystal surface and subsequent thermal annealing. By means of low-energy electron diffraction intensity (LEED-IV) structural analysis, we show that the obtained 3×3R30° superstructure is in fact a TePd2 surface alloy. Attempts to produce a PdTe2 layer in ultra-high vacuum by increasing the Te content on the surface were not successful.

Angle-resolved X-ray photoelectron spectroscopy intensity modeling of SiNx ultrathin layer grown on Si (100) and Si (111) substrates by N2 plasma treatment

In this work, we investigate the silicon nitridation process using a N2 plasma Glow Discharge Source (GDS) in an ultra-high vacuum chamber. In situ Angle Resolved X-ray Photoelectron Spectroscopy (ARXPS) measurements were performed to determine various chemical environments of the surface species. The main goals of this study are determination of the film chemical composition, to estimate its thickness and identify various phenomena taking place during the nitridation process under different experimental conditions. To achieve these objectives, we developed an ARXPS intensity model for an ultrathin SiNx overlayer. Based on the ARXPS results, which indicate that the silicon nitride film is not homogenous, we adopted a bi-layer model composed of two SixNyOz layers with varying thickness and chemical composition. The model is built from analysis of photoelectron intensities, considering a comparison between experimental and theoretical data. This bi-layer model revealed that the silicon nitride layer consists of a surface layer composed of approximately equal amounts of silicon and nitrogen (50% each), and an interfacial layer containing varying amounts of oxygen depending on experimental parameters. The presence of oxygen is due to residual air contamination in the vacuum chamber and/or to Si native oxide. The estimated thickness of silicon nitride film is less than 9 nm, depending on the nitridation time and temperature.The model developed in this work enabled us to study the effects of initial surface state (as received or chemically cleaned), Si substrate crystallographic orientation (such as (100) and (111)), and the nitridation temperature (room temperature and 500°C). The diffusing species (N+, N2+, O+), which play a crucial role during nitridation, were found to be influenced by temperature, treatment time, and substrate orientation. The diffusion phenomenon competed with other processes such as NO desorption, leading to a significant impact on formation of the SiNx film. Furthermore, we compared the thickness obtained from the ARXPS model using cross-sectional High-Resolution Transmission Electron Microscopy (HR-TEM) images. Additional Low-Energy Electron Diffraction (LEED) measurements indicated that the SiNx film was amorphous.

Tin Halide Perovskite Epitaxial Films on Gold Surfaces: Atomic Structure and Stability

AbstractTin‐based halide perovskite solar cells can be efficient and environmentally friendly substitutions to lead‐based halide perovskite solar cells, but they have a drawback due to oxidation from Sn2+ to Sn4+. Using vacuum deposition, epitaxially aligned CsSnBr3 ultrathin films are prepared on Au(111) and Au(100) and characterized with scanning tunneling microscopy (STM), low‐energy electron diffraction (LEED), and X‐ray photoelectron spectroscopy (XPS). By co‐evaporation of the precursor molecules CsBr and SnBr2, few monolayers of perovskite are obtained. On Au(111), CsSnBr3 grows in three differently oriented domains due to the hexagonal symmetry of the substrate. On Au(100), which has square symmetry, identical to CsSnBr3, but with about half the lattice constant of the perovskite, a (2×2) superstructure is observed. The perovskite is terminated with the (001) facet showing a square surface structure in agreement with density functional theory (DFT) calculations. Chemical analysis is performed in ultra‐high vacuum (UHV) conditions and no indication of a tin oxidation state higher than Sn2+ is found in the films. However, after exposure to air, rapid and severe changes in the films are observed, highlighting the importance of preparing tin perovskites in a controlled environment to maintain their stability and avoid oxidation‐related issues.

Electron screening length identifying circular dichroism of photoemission

Circular dichroism angle-resolved photoemission spectroscopy (CD-ARPES) receives much attention due to a resolving power of topological and quantum geometrical nature of two-dimensional systems. We propose the Lippmann-Schwinger photoelectron final state, a scattering solution of the lattice model comprising screened short-range potentials at periodically arranged atomic sites, which characterizes the time-reversed low energy electron diffraction (LEED) state well enough to describe the final state effect entailed in CD-ARPES. We find that, through the final state effect, the electron screening length identifies CD-ARPES not only in the qualitative dichroic polarity but also in the quantitative dichroic strength in various graphene systems like the monolayer graphene, the AA-stacking bilayer graphene, and the twisted bilayer graphene especially in a unified fashion. This finding reveals an interplay between electron screening and circular dichroism and enables to extend the spectroscopic expertise of CD-ARPES to a direct probe of the electron screening.

Crystallographic faceting of bulk tungsten surfaces observed during in situ heating in an environmental scanning electron microscope

The surface faceting of metals has been studied for several decades, typically using experimental methods such as low-energy electron diffraction. In the current paper, surface faceting of tungsten pellets was studied during in situ heating inside an environmental scanning electron microscope (ESEM), which allowed for direct, high-fidelity observation of morphological changes in response to high-temperature annealing under a moderate vacuum (0.8 Torr). Additionally, a second set of tungsten samples was annealed in an ultrahigh vacuum chamber (10−8 Torr), albeit without direct observation via ESEM. This study revealed that oxygen plays a crucial role in tungsten surface faceting and in a morphological transition to vertex rounding. Furthermore, this paper discusses relevant techniques for identifying the crystallographic indices of surface facets. It is demonstrated that a combination of electron backscatter diffraction, tilted-sample imaging from multiple angles, and serial sectioning in a focused ion beam system can be effectively deployed to determine the geometry of faceting, which in turn can be verified with the aid of software for generating Wulff shapes. The influence of processing environment on tungsten surface faceting enables the possibility of designing and controlling the morphology and crystallographic facets of tungsten surfaces.

Si(111) islands on β-phase Si(111)√3 × √3R30°-Bi

β-phase √3 × √3R30°-bismuth (Bi) on silicon (Si)(111)7 × 7 surface has been exploited as a template for growing Si films. Two-dimensional Si islands with √3 × √3 reconstruction, parallel to that of Si(111)√3 × √3R30°-Bi, have been resolved by means of scanning tunneling microscopy, grazing-incidence X-ray diffraction (XRD) and low electron energy diffraction. Auger electron spectroscopy and scanning tunneling spectroscopy gave interesting electronic features on two-dimensional Si islands, with the evidence of a reduced band gap to ~0.55 eV, related to the presence of the underneath Bi layer, and atomic structural properties typical of Si(111). These experimental findings fully confirm the recently reported calculation based on the first-principles density functional theory, on the prediction of Si(111) growth on top of β-phase √3 × √3R30°-Bi/Si(111)7 × 7 reconstruction, shedding new light on silicon structures.

An approach to surface electron density-sensing property correlation in non-stoichiometric boron carbide

The key to most surface phenomena lies in the surface electron density. Particularly, it is the electron density distribution over the surface that primarily controls the overall interaction of the material with the external environment, say in processes like heterogeneous catalysis. Hence, a precise understanding of surface electron density is essential to understand and design improved surface active materials for catalysis and sensing. Surface structure has been determined primarily using surface sensitive techniques like high-energy surface x-ray diffraction (XRD), the crystal truncation rod scattering method, low-energy electron diffraction, scanning transmission electron microscopy, and grazing incidence small angle x-ray scattering. In this work, using aspherical electron density models of crystal structures in different molecular and extended solids, we show a convenient and complementary way of determining high-resolution experimental surface electron density distribution from conventional bulk x-ray diffraction data. The usefulness of our method has been validated by the surface functionality of boron carbide. While certain surfaces in boron carbide show the presence of substantial electron deficient centers, they are absent in others. Based on that, a new surface property of boron carbide has been inferred and has also been validated by chemiresistive gas sensing experiments.

Robust Dipolar Layers between Organic Semiconductors and Silver for Energy-Level Alignment.

The interface between a metal electrode and an organic semiconductor (OS) layer has a defining role in the properties of the resulting device. To obtain the desired performance, interlayers are introduced to modify the adhesion and growth of OS and enhance the efficiency of charge transport through the interface. However, the employed interlayers face common challenges, including a lack of electric dipoles to tune the mutual position of energy levels, being too thick for efficient electronic transport, or being prone to intermixing with subsequently deposited OS layers. Here, we show that monolayers of 1,3,5-tris(4-carboxyphenyl)benzene (BTB) with fully deprotonated carboxyl groups on silver substrates form a compact layer resistant to intermixing while capable of mediating energy-level alignment and showing a large insensitivity to substrate termination. Employing a combination of surface-sensitive techniques, i.e., low-energy electron microscopy and diffraction, X-ray photoelectron spectroscopy, and scanning tunneling microscopy, we have comprehensively characterized the compact layer and proven its robustness against mixing with the subsequently deposited organic semiconductor layer. Density functional theory calculations show that the robustness arises from a strong interaction of carboxylate groups with the Ag surface, and thus, the BTB in the first layer is energetically favored. Synchrotron radiation photoelectron spectroscopy shows that this layer displays considerable electrical dipoles that can be utilized for work function engineering and electronic alignment of molecular frontier orbitals with respect to the substrate Fermi level. Our work thus provides a widely applicable molecular interlayer and general insights necessary for engineering of charge injection layers for efficient organic electronics.

Tin oxide thin films on Ag(111): Thickness and temperature dependent study of surface structure and electronic properties

Growth and structure of tin oxide films on Ag(111) from submonolayer to 10 monolayer equivalent thickness have been studied using low energy electron diffraction (LEED), x-ray photoemission spectroscopy (XPS) and angle-resolved photoemission spectroscopy techniques for room temperature (RT) and high temperature (HT) (573 K). For RT growth, most of the tin is oxidised to form tin oxide (SnOx) as confirmed by XPS where no metallic component is noticed. However, the grown films are not epitaxial or ordered which can be confirmed by no spots in LEED for higher coverage. Metallic Sn along with two oxidation states of Sn are noticed for HT growth, with the surface mainly composed of SnO2. LEED pattern shows the presence of c(2 × 2) and (3 × 1) along with two different hexagonal multidomain type patterns. The electronic structure for lower coverage resembled the Sn/Ag(111) alloy structures for lower coverage. For higher coverages appearance of three bands below 2 eV binding energy was noticed.

Electronic structure of superconducting VN(111) films

Vanadium nitride (VN) is a transition-metal nitride with remarkable properties that have prompted extensive experimental and theoretical investigations in recent years. However, there is a current paucity of experimental research investigating the temperature-dependent electronic structure of single-crystalline VN. In this study, high-quality VN(111) films were successfully synthesized on α\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\alpha$$\\end{document}-Al2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_2$$\\end{document}O3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_3$$\\end{document}(0001) substrates using magnetron sputtering. The crystal and electronic structures of the VN films were characterized by a combination of high-resolution X-ray diffraction, low-energy electron diffraction, resonant soft X-ray absorption spectroscopy, and ultraviolet photoelectron spectroscopy. The electrical transport measurements indicate that the superconducting critical temperature of the VN films is around 8.1 K. Intriguingly, the temperature-dependent photoelectron spectroscopy measurements demonstrate a weak temperature dependence in the electronic structure of the VN films, which is significant for understanding the ground state of VN compounds.