Low-energy Electron Microscopy Research Articles

Reversible Intercalation of Organic Solvents in Graphite and Its Hindrance by a Strongly Adsorbing Supramolecular Monolayer

AbstractAt elevated temperatures, the prototypical organic solvents used to study the self‐assembly of supramolecular monolayers at liquid–solid interfaces alter a graphite substrate by intercalation. As a consequence, less strongly bound supramolecular monolayers become thermodynamically unstable, as probed by scanning tunneling microscopy. Complementary characterization by atomic force microscopy, confocal Raman spectroscopy and low energy electron microscopy consistently points to subsurface changes in the top few layers of the graphite substrate due to solvent intercalation. High‐temperature annealing at 900 °C in the vacuum restores the adsorption properties of the graphite substrates, indicating a high activation energy for deintercalation. However, strongly adsorbing hydrogen‐bonded monolayers of trimesic acid inhibit solvent intercalation and thus protect the graphite substrate. Mildly solvent‐intercalated graphite may prove useful as an easily prepared graphitic material with further weakened adsorption properties.

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. 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 fate of graphene on copper: Intercalation / de-intercalation processes and the role of silicon

Intercalation and de-intercalation processes below graphene (g) grown by chemical vapor deposition (CVD) on Cu foils (g/Cu) were investigated in a combined low-energy electron microscopy and X-ray photoemission electron microscopy study. Exposure of g/Cu to air induces oxygen and water intercalation which can be removed by annealing in vacuum leading to clean and well-ordered graphene on Cu. However, prolonged air exposure leads to intercalation of large amounts of oxygen, most likely inducing the formation of copper oxides. If sufficient intercalated oxygen remains at the interface when exceeding 320 °C, graphene is oxidized and burned off. Cu foils can be loaded with silicon on purpose during foil pre-treatment or accidently during long growth time when applying high temperatures at elevated H2 pressure inducing the reactive removal of Si species from the quartz reactor wall. Due to the dissolution of Si in the Cu bulk, the Si surface concentration remains below detection limit and graphene of equal crystalline quality is grown as if the Cu foil was silicon-free. However, oxygen intercalation underneath graphene on Si-containing Cu foils can induce Si segregation towards the surface and formation of intercalated silica without attacking the covering graphene. Even at high temperatures, segregating Si acts as oxygen scavenger so that graphene resists oxidation. The observed effect explains the usefulness of certain synthesis protocols and paves the way towards large-scale fabrication of electronically decoupled graphene. The effect can be used to immobilize adsorbing oxygen at the interface and image the initial steps of intercalation below graphene in-situ.

A soft touch with electron beams: Digging out structural information of nanomaterials with advanced scanning low energy electron microscopy coupled with deep learning

Nanostructured materials continue to find applications in various electronic and sensing devices, chromatography, separations, drug delivery, renewable energy, and catalysis. While major advancements on the synthesis and characterization of these materials have already been made, getting information about their structures at sub-nanometer resolution remains challenging. It is also unfortunate to find that many emerging or already available powerful analytical methods take time to be fully adopted for characterization of various nanomaterials. The scanning low energy electron microscopy (SLEEM) is a good example to this. In this report, we show how clearer structural and surface information at nanoscale can be obtained by SLEEM, coupled with deep learning. The method is demonstrated using Au nanoparticles-loaded mesoporous silica as a model system. Moreover, unlike conventional scanning electron microscopy (SEM), SLEEM does not require the samples to be coated with conductive films for analysis; thus, not only it is convenient to use but it also does not give artifacts. The results further reveal that SLEEM and deep learning can serve as great tools to analyze materials at nanoscale well. The biggest advantage of the presented method is its availability, as most modern SEMs are able to operate at low energies and deep learning methods are already being widely used in many fields.

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.

Energy-dispersive X-ray spectroscopy in a low energy electron microscope

Energy-Dispersive X-Ray Spectroscopy (EDS) is a technique frequently used in Scanning and Transmission Electron Microscopes to study the elemental composition of a sample. Briefly, high energy electrons of the incident electron beam may ionize an electron from a core shell. The decay of this excited state may result in the emission of a characteristic X-ray photon or Auger-Meitner electron. A solid-state EDS detector captures the X-ray photon and determines its energy. The energy spectrum thus contains information on the elemental make-up of the sample. Low Energy Electron Microscopy (LEEM) typically utilizes incident electrons with energies in the range 0–100 eV, insufficient for the generation of elemental X-rays. In general, LEEM does therefore not allow for elemental characterization of the sample under study. Here we show how relatively simple modifications and additions to the LEEM instrument make in-situ EDS spectroscopy possible, and how high-quality EDS spectra can be obtained, thus enabling elemental analysis in LEEM instruments for the first time.

Towards quantification of doping in gallium arsenide nanostructures by low-energy scanning electron microscopy and conductive atomic force microscopy.

We calculate a universal shift in work function of 59.4 meV per decade of dopant concentration change that applies to all doped semiconductors and from this use Monte Carlo simulations to simulate the resulting change in secondary electron yield for doped GaAs. We then compare experimental images of doped GaAs layers from scanning electron microscopy and conductive atomic force microscopy. Kelvin probe force microscopy allows to directly measure and map local work function changes, but values measured are often smaller, typically only around half, of what theory predicts for perfectly clean surfaces.

Thermomechanic behavior of epitaxial GeTe ferroelectric films

A key development toward new electronic devices integrating memory and processing capabilities could be based on the electric control of the spin texture of charge carriers in semiconductors. In that respect, GeTe has been recently recognized as a promising ferroelectric Rashba semiconductor, with giant spin splitting of the band structure, due to the inversion symmetry breaking arising from ferroelectric polarization. Here, we address the temperature dependence of the ferroelectric structure of GeTe thin films grown on Si(111). We demonstrate the hysteretic behavior of the ferroelectric domain density upon heating/cooling cycles by low energy electron microscopy. This behavior is associated with an abnormal evolution of the GeTe lattice parameter as shown by x-ray diffraction. We explain these thermomechanical phenomena by a large difference of thermal expansion coefficients between the film and the substrate and to the pinning of the GeTe/Si interface. The accumulated elastic energy by the GeTe thin film during sample cooling is released by the formation of a-nanodomains with in-plane ferroelectric polarization components.

Angle-resolved photoelectron spectroscopy in a low-energy electron microscope.

Spectroscopic photoemission microscopy is a well-established method to investigate the electronic structure of surfaces. In modern photoemission microscopes, the electron optics allow imaging of the image plane, momentum plane, or dispersive plane, depending on the lens setting. Furthermore, apertures allow filtering of energy-, real-, and momentum space. Here, we describe how a standard spectroscopic and low-energy electron microscope can be equipped with an additional slit at the entrance of the already present hemispherical analyzer to enable an angle- and energy-resolved photoemission mode with micrometer spatial selectivity. We apply a photogrammetric calibration to correct for image distortions of the projective system behind the analyzer and present spectra recorded on Au(111) as a benchmark. Our approach makes data acquisition in energy-momentum space more efficient, which is a necessity for laser-based pump-probe photoemission microscopy with femtosecond time resolution.

Peculiar Structural Phase of a Single-Atom-Thick Layer of Antimony.

Using molecular beam epitaxy, a new structural phase of a single atom thick antimony layer has been synthesized on the W(110) surface. Scanning tunneling microscopy measurements reveal an atomically resolved structure with a perfectly flat surface and unusually large unit cell. The structure forms a well-ordered continuous film with a lateral size in the range of several millimeters, as revealed by low energy electron microscopy and diffraction experiments. The results of density functional theory calculations confirm the formation of a new phase of single-atom-thick antimony film without the buckling characteristic for the known phases of antimonene. The presented results demonstrate a substrate-tuned approach in the preparation of new structural phases of 2D materials.

Spectromicroscopic study of the transformation with low energy ions of a hematite thin film into a magnetite/hematite epitaxial bilayer

The search of new properties in novel oxide heterostructures requires the exploration of new fabrication methods and the study, at the microscopic level, of the processes involved during the synthesis. We present a synchrotron-based spectromicroscopic investigation of a magnetite/hematite bilayer on Pt(111) grown in a two-step process by thermal evaporation and Low Energy Ion Bombardment (LEIB). The characterization includes the study of structural, electronic, chemical, and magnetic properties using X-ray Absorption Spectroscopy (XAS), Low Energy Electron Microscopy (LEEM), Photoemission Electron Microscopy (PEEM), or X-ray Magnetic Circular Dichroism (XMCD). The aim is to obtain microscopic information of the thin film before, during, and after the ion bombardment. Ion bombardment gradually transforms the topmost layers of the hematite thin film into a defective sub-oxide, where magnetite nuclei grow and coalesce with increasing ion doses. Two rotational domains of magnetite coexist, which are typically a few tens of nanometres large and do not grow significantly with temperature annealings. The incoherent growth of the magnetite nuclei favours the formation of stable twin boundaries (TBs) and antiphase boundaries (APBs). Dichroic spectra show the characteristics of the ferrimagnetic (FiM) order of magnetite, and the spatial distribution of magnetic domains shows no apparent correlation with the structural image, displaying smooth domains separated by diffuse frontiers. These findings illustrate the importance of a spectromicroscopic characterization of novel oxide heterostructures for potential future applications.

Determination of the Thermomigration Force on Adatoms.

Thermal gradients in nanomaterials can cause surface mass transport phenomena. However, the atomic fluxes are challenging to quantify and the underlying atomic mechanisms are complex. Using low energy electron microscopy we have examined in operando, under a thermal gradient of 10^{4} K/m, the thermomigration of supercooled Si(111)-1×1 advacancy islands. The islands move in the direction of the thermal gradient at 0.26±0.06 nm/s. This reveals that the adatoms move toward the cold region and the effective force exerted on Si adatoms is 1.4±0.4×10^{-8} eV/nm. We quantify the heat of transport of Si atoms Q^{*}=1.2±0.4 eV and show that it corresponds to the combined effects of adatom creation at step edges and adatom diffusion on atomically flat terraces.

Nanosized antiferromagnetic domains in NiO/Ag(001) films probed by polarised X-ray and unpolarised low-energy electrons

Surface antiferromagnetism of NiO film, epitaxially deposited on Ag(001), is investigated using the absorption of linearly polarised X-ray and the diffraction of low-energy unpolarised electrons. Polarisation-dependent X-ray absorption studies reveal a preferential stabilisation of the magnetic domains with the main components of magnetic axes parallel to the interface. Furthermore, the role of interfacial strain-induced magnetocrystalline anisotropy below a critical film thickness (∼ 20 ML) could be demonstrated by the magnetic linear dichroism results. Utilising the exchange scattered electrons from various antiferromagnetic (111) planes, the magnetic twin domains could be probed by a low energy electron microscope operating in the dark-field mode. The linearly polarised X-ray, on the other hand, is sensitive to the magnetic axes orientations of Ni2+ ions and therefore, provides access to the spin domains as well as the twin domains. Comparison of results of these two independent imaging techniques demonstrates that the in-plane component of the magnetic easy axes contained by the complementary T-domains are parallel to each other.

Interplay of Kinetic Limitations and Disintegration: Selective Growth of Hexagonal Boron Nitride and Borophene Monolayers on Metal Substrates.

The CVD growth of bielemental 2D-materials by using molecular precursors involves complex formation kinetics taking place at the surface and sometimes also subsurface regions of the substrate. Competing microscopic processes fundamentally limit the parameter space for optimal growth of the desired material. Kinetic limitations for diffusion and nucleation cause a high density of small domains and grain boundaries. These are usually overcome by increasing the growth temperature and decreasing the growth rate. In contrast, the nature of molecular precursors with limited thermal stability can result in dissociation and preferential desorption, leading to an undesired or ill-defined composition of the 2D-material. Here we demonstrate these constraints in a combined low-energy electron diffraction and low-energy electron microscopy study by examining the selective formation of single-layer hexagonal boron nitride (hBN) and borophene on Ir(111) using a borazine precursor. We derive a temperature-pressure phase diagram and apply classical nucleation theory to describe our results. By considering the competing processes, we find an optimum growth temperature for hBN of 950 °C. At lower temperatures, the hBN island density is increased, while at higher temperatures the precursor disintegrates and borophene is formed. Our results introduce an additional aspect that must be considered in any high-temperature growth of bielemental 2D-materials from single molecular precursors.

Aperiodic Modulation of Graphene Driven by Oxygen-Induced Reconstruction of Rh(110).

Artificial nanostructuring of graphene has served as a platform to induce variations in its structural and electronic properties, fostering the experimental observation of a wide and fascinating phenomenology. Here, we present an approach to graphene tuning, based on Rh(110) surface reconstruction induced by oxygen atoms intercalation. The resulting nanostructured graphene has been characterized by scanning tunneling microscopy (STM) complemented by low-energy electron microscopy (LEEM), micro low-energy electron diffraction (μ-LEED), micro angle-resolved photoemission spectroscopy (μ-ARPES), and micro X-ray photoelectron spectroscopy (μ-XPS) measurements under ultrahigh vacuum (UHV) conditions at room temperature (RT). It is found that by fine-tuning the O2 exposure amount, a mixture of missing row surface reconstructions of the metal surface below the graphene layer can be induced. This atomic rearrangement under the graphene layer results in aperiodic patterning of the two-dimensional (2D) material. The electronic structure of the resulting nanostructured graphene is dominated by a linear dispersion of the Dirac quasiparticles, characteristic of its free-standing state but with a p-doping character. The local effects of the underlying missing rows on the interfacial chemistry and on the quasiparticle scattering processes in graphene are studied using atomically resolved STM images. The possibilities offered by this nanostructuring approach, which consists in inducing surface reconstructions under graphene, could provide a novel tuning strategy for this 2D material.

Cr silicate as a prototype for engineering magnetic phases in air-stable two-dimensional transition-metal silicates

Identifying environmentally inert, ferromagnetic two-dimensional (2D) materials with high Curie temperatures (T c) down to the single layer limit has been an obstacle to fundamental studies of 2D magnetism and application of 2D heterostructures to spin-polarized devices. To address this challenge, the growth, structure and magnetic properties of a 2D Cr-silicate single layer on Pt(111) was investigated experimentally and theoretically. The layer was grown by sequentially depositing SiO and Cr followed by annealing in O2. Scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and low energy electron microscopy all indicated a well-ordered layer that uniformly covered the surface, with STM and LEED indicating that the silicate relaxed to its favored lattice constant. Further experimental characterizations demonstrated that the Cr was nominally 3+ but with a lower electron density than typical trivalent Cr compounds. Comparison with theory identified a Cr2Si2O9 structure that resembles a single layer of a dehydrogenated dioctahedral silicate. Magnetic circular dichroism in x-ray absorption spectroscopy revealed a ferromagnetically ordered state up to at least 80 K. Theoretical analysis revealed that the Cr in a dehydrogenated Cr-silicate/Pt(111) is more oxidized than Cr in freestanding Cr2Si2O9H4 layers. This greater oxidation was found to enhance ferromagnetic coupling and suggests that the magnetism may be tuned by doping. The 2D Cr-silicate is the first member of a broad series of possible layered first-row transition metal silicates with magnetic order; thus, this paper introduces a new platform for investigating 2D ferromagnetism and the development of magnetoelectronic and spintronic devices by stacking 2D atomic layers.

Direct Visualization of the Charge Transfer in a Graphene/α-RuCl3 Heterostructure via Angle-Resolved Photoemission Spectroscopy.

We investigate the electronic properties of a graphene and α-ruthenium trichloride (α-RuCl3) heterostructure using a combination of experimental techniques. α-RuCl3 is a Mott insulator and a Kitaev material. Its combination with graphene has gained increasing attention due to its potential applicability in novel optoelectronic devices. By using a combination of spatially resolved photoemission spectroscopy and low-energy electron microscopy, we are able to provide a direct visualization of the massive charge transfer from graphene to α-RuCl3, which can modify the electronic properties of both materials, leading to novel electronic phenomena at their interface. A measurement of the spatially resolved work function allows for a direct estimate of the interface dipole between graphene and α-RuCl3. Their strong coupling could lead to new ways of manipulating electronic properties of a two-dimensional heterojunction. Understanding the electronic properties of this structure is pivotal for designing next generation low-power optoelectronics devices.

Contrast mechanism at landing energy near 0 eV insuper low-energy scanning electron microscopy.

In recent years, the technique of scanning electron microscopy (SEM) observation with low landing energy of a few keV or less has become common. We have especially focused on the drastic contrast change at near 0 eV. Using a patterned sample consisting of Si, Ni and Pt, threshold energies where the total reflection of incident electrons occurs were investigated by SEM at near 0 eV. In both the cases of in-situ and ex-situ sample cleaning, drastic changes in the brightness of each material were observed at near 0 eV, with threshold energies in the order Si < Ni < Pt. This order agreed with the order of the literature values of the work functions and the surface potentials measured by Kelvin force probe microscopy. This result suggests that the difference of the threshold energy is caused by the difference in surface potential due to the work function difference of each material. Although the order of the threshold energies also agreed with those of work functions reported in the literature, the work functions of air-exposed surfaces should be rather considered as 'modified work functions', since they could be significantly altered by the adsorbates, etc. Nevertheless, the difference of the threshold energy for each material was observed with commercial SEM at landing energy near 0 eV, which opens a new possibility to distinguish materials, although the difference should be rather recognized as 'fingerprints', since surface potentials are sensitive to conditions of surface treatments and atmospheric exposure.

Thermal Instability of Gold Thin Films

The disintegration of a continuous metallic thin film leads to the formation of isolated islands, which can be used for the preparation of plasmonic structures. The transformation mechanism is driven by a thermally accelerated diffusion that leads to the minimalization of surface free energy in the system. In this paper, we report the results of our study on the disintegration of gold thin film and the formation of nanoislands on silicon substrates, both pure and with native silicon dioxide film. To study the processes leading to the formation of gold nanostructures and to investigate the effect of the oxide layer on silicon diffusion, metallic film with a thickness of 3 nm was deposited by molecular beam epitaxy (MBE) technique on both pure and oxidized silicon substrates. Transformation of the thin film was observed by low-energy electron microscopy (LEEM) and a scanning electron microscope (SEM), while the nanostructures formed were observed by atomic force microscope (AFM) method. Structural investigations were performed by low-energy electron diffraction (LEED) and X-ray photoelectron spectroscopy (XPS) methods. Our experiments confirmed a strong correlation between the formation of nanoislands and the presence of native oxide on silicon substrates.

Dynamic topological domain walls driven by lithium intercalation in graphene.

Stacking engineering in van der Waals (vdW) materials is a powerful method to control topological electronic phases for quantum device applications. Atomic intercalation into the vdW material can modulate the stacking structure at the atomic scale without a highly technical protocol. Here we report that lithium intercalation in a topologically structured graphene/buffer system on SiC(0001) drives dynamic topological domain wall (TDW) motions associated with stacking order change by using an in situ aberration-corrected low-energy electron microscope in combination with theoretical modelling. We observe sequential and selective lithium intercalation that starts at topological crossing points (AA stacking) and then selectively extends to AB stacking domains. Lithium intercalation locally changes the domain stacking order to AA and in turn alters the neighbouring TDW stacking orders, and continuous intercalation drives the evolution of the whole topological structure network. Our work reveals moving TDWs protected by the topology of stacking and lays the foundation for controlling the stacking structure via atomic intercalation. These findings open up new avenues to realize intercalation-driven vdW electronic devices.