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Understanding of thin film growth mechanism is crucial for tailoring film growth behaviors, which in turn determine physicochemical properties of the resulting films. Here, vapor-growth of tungsten carbide overlayers on W(110) surface is investigated by real time low energy electron microscopy. The surface growth is strongly confined by surface steps, which is in contrast with overlayer growth crossing steps in a so-called carpet-like growth mode for example in graphene growth on metal surfaces. Density functional theory calculations indicate that the step-confined growth is caused by the strong interaction of the forming carbide overlayer with the substrate blocking cross-step growth of the film. Furthermore, the tungsten carbide growth within each terrace is facilitated by the supply of carbon atoms from near-surface regions at high temperatures. These findings suggest the critical role of near-surface atom diffusion and step confinement effects in the thin film growth, which may be active in many film growth systems.

This work illustrates the impact of atmospheric gases on the surface of epitaxial graphene. The different rate of adsorption on different parts of graphene samples provides a concrete evidence that the surface morphology of graphene plays a significant role in this process. The uneven adsorption occurs only on the surface of the monolayer graphene and not on bilayer graphene. The second monolayer is distinguished and verified by the phase contrast mode of atomic force microscopy and the low energy electron microscopy, respectively. Raman spectroscopy is used to study the strain on the surface of graphene; results indicate that monolayer and bilayer graphene exhibit different types of strain. The bilayer is under more compressive strain in comparison with monolayer graphene that hinders the process of adsorption. However, the wrinkles and edges of steps of the bilayer are under tensile strain, hence, facilitate adsorption. Samples were subjected to X-ray photoelectron spectroscopy which confirms that the adsorbates on the epitaxial graphene are carbon clusters with nitrogen and oxygen contamination. For reversing the adsorption process the samples are annealed and a method for the removal of these adsorbates is proposed.

The characterization and control of atomic substitution process is crucial in fabricating high-quality two-dimensional layered compound materials and tuning their physical properties. With intensity-voltage low energy electron microscopy (IV-LEEM), we found that the concentration of copper in the topmost copper silicide monolayer on Si (111) substrates varies gradually from 1.7 to 1.0 ML while preserving it's unique ′5 × 5′ incommensurate phase in a transition region as large as 1000 nm. This gradual variation of the copper concentration is due to the incomplete substitution of the Si with Cu, as revealed by atomic-resolved scanning tunneling microscopy with a tip that nicely resolved the ′5 × 5′ periodicity. Our experiments indicate that besides the widely-accepted phase of Cu2Si with both substitutional and interstitial Cu atoms, another type of precursor copper silicide CuSi3 with only interstitial Cu atoms also plays important roles in the substitutional diffusion and reaction processes during the formation of the topmost copper silicide monolayer. This precursor phase might exist in the growth of other two-dimensional layered materials with potential applications in integrated optoelectronics, spintronics or low dissipative devices.

Transmission electron microscopy at very low energy is a promising way to avoid damaging delicate biological samples with the incident electrons, a known problem in conventional transmission electron microscopy. For imaging in the 0-30 eV range, we added a second electron source to a low energy electron microscopy (LEEM) setup, enabling imaging and spectroscopy in both transmission and reflection mode at nanometer (nm) resolution. The latter is experimentally demonstrated for free-standing graphene. Exemplary eV-TEM micrographs of gold nanoparticles suspended on graphene and of DNA origami rectangles on graphene oxide further establish the capabilities of the technique. The long and short axes of the DNA origami rectangles are discernable even after an hour of illumination with low energy electrons. In combination with recent developments in 2D membranes, allowing for versatile sample preparation, eV-TEM is paving the way to damage-free imaging of biological samples at nm resolution.

Miniaturization of electronic devices and progress in surface science demand novel, powerful microscopy methods for material characterization on a length scale of only a few atomic distances. This paper discusses application of the combined x-ray photoelectron microscopy / low-energy electron microscopy (XPEEM/LEEM) system to studying of the structural, electronic and chemical properties of surfaces at nanometer scale. Several examples are given, focusing on the comprehensive spectro-microscopic investigations of 2D structures, including epitaxially grown films as well as exfoliated, μm-size thin flakes of 2D van der Waals materials. Benefitting from the high brilliance of the synchrotron, and utilizing its capabilities for in-situ sample preparation and treatment, the XPEEM/LEEM is a powerful tool for comprehensive characterization of static and dynamic properties of surfaces and interfaces, and it is particularly suited for comprehensive investigation of 2D materials, down to single monolayers.

Two-dimensional materials, such as graphene, are usually prepared by chemical vapor deposition (CVD) on selected substrates, and their transfer is completed with a supporting layer, mostly polymethyl methacrylate (PMMA). Indeed, the PMMA has to be removed precisely to obtain the predicted superior properties of graphene after the transfer process. We demonstrate a new and effective technique to achieve a polymer-free CVD graphene — by utilizing low-energy electron irradiation in a scanning low-energy electron microscope (SLEEM). The influence of electron-landing energy on cleaning efficiency and graphene quality was observed by SLEEM, Raman spectroscopy (the presence of disorder D peak) and XPS (the deconvolution of the C 1s peak). After removing the absorbed molecules and polymer residues from the graphene surface with slow electrons, the individual graphene layers can also be distinguished outside ultra-high vacuum conditions in both the reflected and transmitted modes of a scanning low-energy (transmission) electron microscope.

Two-dimensional group IV monochalcogenide semiconductors (SnX, GeX; X = S, Se) are of fundamental interest due to their anisotropic crystal structure and predicted unique characteristics such as very large exciton binding energies and multiferroic order possibly up to above room temperature. Whereas growth on reactive supports produces mostly standing flakes, deposition on van der Waals (vdW) substrates can yield basal-plane oriented layered crystals. But so far, this approach invariably resulted in flakes that are several atomic layers thick, and the synthesis of monolayers has remained elusive. Here, we use in situ microscopy during molecular beam epitaxy of SnS on graphite and graphene to establish the origin of this predominant multilayer growth. The enhanced reactivity of group IV chalcogenide layers causes adsorption of precursor molecules primarily on the initial SnS nuclei instead of the vdW support. On graphite, this unusual imbalance in the material supply is the primary cause for fast vertical ...

Thin, stable and inert dielectric spacers are essential for manufacturing electronic devices based on 2D materials. However, direct synthesis on top of 2D materials is difficult due to their inert nature. In this work, we studied how an electron beam induces fragmentation of borazine and enables spatially confined synthesis of amorphous-BNx on graphene at room temperature. Using a combination of X-ray Photoelectron Spectroscopy, Low Energy Electron Microscopy, and Scanning Tunneling Microscopy we studied the morphology of the heterostructure, its chemical composition, and finally its temperature evolution. We find that electron-beam induced deposition starts by the binding of heavily fragmentized borazine, including atomic boron, followed by the growth of a multilayer with a 1:0.7 B:N ratio. The final structure exhibits a thermal stability up to 1400 K and ~ 50 nm spatial control provided by the electron beam. Our studies provide surface science insight into the use of electron beams for synthesis and lateral control of stable and inert layers in 2D heterostructures.

A theoretical understanding of image formation in cathode lens microscopy can facilitate image interpretation. We compare Fourier Optics (FO) and Contrast Transfer Function (CTF) approaches that were recently adapted from other realms of microscopy to model image formation in low energy electron microscopy (LEEM). Although these two approaches incorporate imaging errors from several sources similarly, they differ in the way that the image intensity is calculated. The simplification that is used in the CTF calculation advantageously leads to its computational efficiency. However, we find that lens aberrations, and spatial and temporal coherence may affect the validity of the CTF approach to model LEEM image formation under certain conditions. In particular, these effects depend strongly on the nature of the object being imaged and also become more pronounced with increasing defocus. While the use of the CTF approach appears to be justified for objects that are routinely imaged with LEEM, comparison of theory to experimental observations of a focal image series for rippled, suspended graphene reveals one example where FO works, but CTF does not. This work alerts us to potential pitfalls and guides the effective use of FO and CTF approaches. It also lays the foundation for quantitative image evaluation using these methods.

Accurately measuring defocus in cathode lens instruments (Low Energy Electron Microscopy - LEEM, and Photo Electron Emission Microscopy - PEEM) is a pre-requisite for quantitative image analysis using Fourier Optics (FO) or Contrast Transfer Function (CTF) image simulations. In particular, one must establish a quantitative relation between lens excitation and image defocus. One way to accomplish this is the Real-Space Microspot LEED method, making use of the accurately known angles of diffracted electron beams, and the defocus-dependent shifts of their corresponding real-space images. However, this only works if a sufficiently large number of diffracted beams is available for the sample under investigation. An alternative is to shift the sample along the optical axis by a known distance, and measure the change in objective lens excitation required to re-focus the image. We analytically derive the relation between sample shift and defocus, and apply our results to the measurement and analysis of achromats in an aberration-corrected LEEM instrument.

The growth of low-dimensional nanostructures of Au on Ge(1 1 0) and their temperature-induced motion were observed with Low Energy Electron Microscopy (LEEM). Ge(1 1 0) was dosed with 0.5–4 ML of Au and heated to 850 °C. Above 500 °C, liquid AuGe eutectic alloy islands grew on the surface. Islands were 0.3–3.0 µm in width, 1–10 µm in length, and elongated in the [ 1 1 ¯ 0 ] direction. Above 600 °C, islands began moving with speeds of 0.1–1.0 µm/s, absorbing smaller stationary islands upon collision and increasing in size to more than 100 µm in width. A temperature gradient of ∼0.017 °C/µm across the sample results in a gradient in the Ge concentration across the islands, inducing their movement in the direction of increasing temperature. Optical microscopy confirmed that the large islands moved from the cooler edges of the sample towards its hotter center. The mechanism for motion of the droplets is discussed, and the island velocities fit well to a model for diffusion-driven motion of the liquid droplet. When the temperature was subsequently lowered, islands became supersaturated with Ge, which crystallized on the island edges.

The growth of Ir on Ge(111) as a function of temperature between 23 °C and 820 °C is characterized with low energy electron microscopy (LEEM), low energy electron diffraction (LEED), scanning tunneling microscopy (STM), and x-ray photoemission spectroscopy (XPS). Deposition onto a substrate at 350 °C revealed a novel growth mode consisting of multilayer Ir islands with (√3 × √3)R30° (abbreviated as √3) structure interconnected by “bridges” of single-layer Ir several atoms wide. For deposition onto substrates above 500 °C, the √3 Ir phase grows with dendritic morphology, and substrate step bunches act as barriers to √3 Ir growth. LEEM images showed Stranski–Krastanov growth for 650–820 °C: after the √3 phase covers the surface, corresponding to 2 monolayers (ML) Ir coverage, multilayer hexagonal-shaped Ir islands form, surrounded by regions of IrGe alloy. Hexagonal-shaped Ir islands also formed upon heating 1.2 ML of √3 Ir beyond 830 °C, which resulted in the elimination of √3 structure from the surface. The transformation from √3 to (1 × 1) structure upon heating to 830 °C was an irreversible surface phase transition. Annealing > 2.0 ML of Ir in the √3 phase above the 830 °C disorder temperature, followed by cooling, produced a (3 × 1) structure. Subsequent heating and cooling through 830 °C give evidence for a reversible (3 × 1) to (1 × 1) phase transition.

Quantized magnetotransport is observed in 5.6 × 5.6 mm2 epitaxial graphene devices, grown using highly constrained sublimation on the Si-face of SiC(0001) at high temperature (1900 °C). The precise quantized Hall resistance of R x y = h 2 e 2 is maintained up to record level of critical current Ixx = 0.72 mA at T = 3.1 K and 9 T in a device where Raman microscopy reveals low and homogeneous strain. Adsorption-induced molecular doping in a second device reduced the carrier concentration close to the Dirac point (n ≈ 1010 cm−2), where mobility of 18760 cm2/V is measured over an area of 10 mm2. Atomic force, confocal optical, and Raman microscopies are used to characterize the large-scale devices, and reveal improved SiC terrace topography and the structure of the graphene layer. Our results show that the structural uniformity of epitaxial graphene produced by face-to-graphite processing contributes to millimeter-scale transport homogeneity, and will prove useful for scientific and commercial applications.

Graphene layers are often exposed to gaseous environments in their synthesis and application processes, and interactions of graphene surfaces with molecules particularly H2 and O2 are of great importance in their physico-chemical properties. In this work, etching of graphene overlayers on Pt(111) in H2 and O2 atmospheres were investigated by in-situ low energy electron microscopy. Significant graphene etching was observed in 10−5 Torr H2 above 1023 K, which occurs simultaneously at graphene island edges and interiors with a determined reaction barrier at 5.7 eV. The similar etching phenomena were found in 10−7 Torr O2 above 973 K, while only island edges were reacted between 823 and 923 K. We suggest that etching of graphene edges is facilitated by Pt-aided hydrogenation or oxidation of edge carbon atoms while intercalation-etching is attributed to etching at the interiors at high temperatures. The different findings with etching in O2 and H2 depend on competitive adsorption, desorption, and diffusion processes of O and H atoms on Pt surface, as well as intercalation at the graphene/Pt interface.

This paper describes a newly designed set-up which is intended for automated preparation both for STM tips and for ultra-sharp field emission cathodes made of polycrystalline and single crystal tungsten in laboratory conditions. The newly designed set-up incorporates electrochemical etching of a wire in the surface layer of an electrolyte and also the so called drop-off method which consists of two steps and requires more precise wire and current setting. Additionally, the method was extended for polycrystalline wires of tungsten using a special cut-off algorithm, which deals with variable etching speed for various crystallographic orientation of the current grain. Produced tips are examined using scanning low energy electron microscopy as for the surface and by the occurrence of electron field-emission as for the geometry based on the Fowler-Nordheim analysis. STM performance of the produced tip is discussed and examined as well.

Silver is one of the most promising cathode materials for low temperature (300–500 °C) solid oxide fuel cells. The most important disadvantage of silver is its migration in the electric field. For better understanding of this phenomenon, an in situ observation of the migration mechanism was undertaken with the use of high-temperature microscopes. Scandia stabilised ceria doped zirconia CeScSZ electrolyte prepared from commercial powder was examined before and after silver migration experiments using scanning electron microscope. X-ray diffraction, broadband electrochemical impedance spectroscopy, and X-ray photoelectron spectroscopy. The silver electrodes for solid oxide fuel cells were prepared using magnetron sputtering. The described cells under polarisation were examined using a high-temperature low energy electron microscope. Reference cells and post-mortem cells were observed using a scanning electron microscope equipped with high temperature stage. Under polarisation, silver moved inside the electrolyte and along the surface towards the region between electrodes. The structures thus formed were similar to those previously described in the literature; however, direct observation of the deposit growth was unsuccessful. In situ scanning electron microscopy observations of the silver electrode at 650 °C revealed neither melting of the smallest silver particles nor movement of silver structures. Silver migration through the electrolyte caused a reduction in grain interior conductivity of the electrolyte, whereas its grain boundary conductivity remained unaffected.

In contrast to the in-plane transport electron mean-free path in graphene, the transverse mean-free path has received little attention and is often assumed to follow the 'universal' mean-free path (MFP) curve broadly adopted in surface and interface science. Here we directly measure transverse electron scattering through graphene from 0 to 25 eV above the vacuum level both in reflection using Low Energy Electron Microscopy and in transmission using electron-Volt Transmission Electron Microscopy. From this data, we obtain quantitative MFPs for both elastic and inelastic scattering. Even at the lowest energies, the total MFP is just a few graphene layers and the elastic MFP oscillates with graphene layer number, both refuting the 'universal' curve. A full theoretical calculation taking the graphene band structure into consideration agrees well with experiment, while the key experimental results are reproduced even by a simple optical toy model.

Low-energy electrons offer a unique possibility for long exposure imaging of individual biomolecules without significant radiation damage. In addition, low-energy electrons exhibit high sensitivity to local potentials and thus can be employed for imaging charges as small as a fraction of one elementary charge. The combination of these properties makes low-energy electrons an exciting tool for imaging charge transport in individual biomolecules. Here we demonstrate the imaging of individual deoxyribonucleic acid (DNA) molecules at the resolution of about 1 nm with simultaneous imaging of the charging of the DNA molecules that is of the order of less than one elementary charge per nanometer. The cross-correlation analysis performed on different sections of the DNA network reveals that the charge redistribution between the two regions is correlated. Thus, low-energy electron microscopy is capable to provide simultaneous imaging of macromolecular structure and its charge distribution which can be beneficial for imaging and constructing nano-bio-sensors.

A novel method to fabricate uniform epitaxial graphene on C-face SiC substrates was investigated. Graphene was grown on the C-face 6H-SiC substrates with a sputtered SiC film by annealing temperatures ranging from 1400 to 1900 °C under an Ar ambient. The fractional area of the graphene having the layer number of two was about 95% in a 75×75 μm square by a Raman mapping and a low energy electron microscopy. Graphene on the C-face SiC fabricated by this method is quite uniform compared to that made by a conventional method without the sputtered SiC films and is thus suitable for high frequency analog devices.

The structural and electronic properties of Pt induced nanowires on Ge(110) surfaces have been studied by scanning tunneling microscopy and low energy electron microscopy. The deposition of a sub-monolayer amount of Pt and subsequent annealing at 1100 (±30) K results into nanowires which are aligned along the densely packed [1–10] direction of the Ge(110) surface. With increasing Pt coverage the nanowires form densely packed arrays with separations of 1.1 ± 0.1 nm, 2.0 ± 0.1 nm and 3.4 ± 0.1 nm. Ge pentagons reside in the troughs for nanowire separations of 3.4 nm, however for smaller nanowire separations no pentagons are found. Spatially resolved scanning tunneling spectroscopy measurements reveal a filled electronic state at −0.35 eV. This electronic state is present in the troughs as well as on the nanowires. The −0.35 eV state has the strongest intensity on the pentagons. For Pt depositions exceeding two monolayers, pentagon free nanowire patches are found, that coexist with Pt/Ge clusters. Upon annealing at 1040 K these Pt/Ge clusters become liquid-like, indicating that we are dealing with eutectic Pt0.22Ge0.78 clusters. Low energy electron microscopy videos reveal the formation and spinodal decomposition of these eutectic Pt/Ge clusters.

The orientation control of graphene overlayers on metal surface is an important issue which remains as a challenge in graphene growth on Ni surface. Here we have demonstrated that epitaxial graphene overlayers can be obtained by annealing a nickel carbide covered Ni(111) surface using in situ surface imaging techniques. Epitaxial graphene islands nucleate and grow via segregation of dissolved carbon atoms to the top surface at about 400 °C. This is in contrast to a mixture of epitaxial and non-epitaxial graphene domains grown directly on Ni(111) at 540 °C. The different growth behaviors are related to the nucleation dynamics which is controlled by local carbon densities in the near surface region.

Graphene and related two-dimensional (2D) materials are attracting huge attention due to their wide-range potential applications. Because large-scale, high-quality 2D crystals are prerequisites for many of the applications, crystal growth of 2D materials has been intensively studied. We have also been conducting research to understand the growth mechanism of 2D materials and have been developing growth techniques of high-quality materials based on the understandings, in which detailed structural characterizations using low-energy electron microscopy (LEEM) have played essential roles. In this paper, we explain the principles of obtaining various structural features using LEEM, and then we review the status of our current understanding on the growth of graphene and hexagonal boron nitride.

A monolayer of graphene was prepared by thermal decomposition of ethylene gas on Pt(111). The graphene can be readily removed by dosing O2 at pressures in 10− 8 mbar range and surface temperatures (Ts) near 1000 K. Residual gas analysis during the oxygen treatment of graphene layer detected CO to be the only formed product. The oxidation process has been continuously imaged by Low-energy Electron Microscope (LEEM) operated in mirror-electron mode. LEEM observations revealed that the oxidation of graphene on Pt(111) occurs simultaneously at the outer island perimeter and in the interior of the graphene island. Symmetric hexagonal pits were observed to form continuously within graphene sheets, the pits proceeded isotropically. The etch rate was determined to be equal for both modes and independent of the surface environment with the exception of areas above Pt step edges. The pit growth rate at constant oxygen pressure was found to increase exponentially with respect to temperature over the investigated Ts range of 927–1014 K, yielding an apparent activation energy of 479 kJ/mol.

Spin Polarized Low Energy Electron Microscopy (SPLEEM) is a powerful tool to reveal the magnetic structure of ferromagnetic surfaces on the atomic depth scale level[1-3]. With aberration corrected LEEM and a high brightness spin polarized electron gun, high spatial resolution will provide more details for ultra-thin ferromagnetic film studies. This study reports the first realization of aberration corrected SPLEEM (AC-SPLEEM). The performance of the setup was tested on ferromagnetic Fe nanoscale islands on a W(110) single crystal, with spatial resolution of 3.3 nm in spin asymmetry images.

Hexagonal boron nitride, often entitled the ‘white graphene’ because of its large band gap, is one of the most important two-dimensional (2D) materials and frequently investigated in context with stacked arrays of single 2D layers, so called van der Waals heterostructures. Here, we concentrate on the growth of hBN on the coinage metal surface Cu(1 1 1). Using low energy electron microscopy and diffraction, we investigate the self-terminated growth of the first layer in situ and in real time. Most prominently, we find dendritic structures with three strongly preferred growth branches that are mostly well aligned with the Cu(1 1 1) substrate and exhibit a three-fold symmetric shape. The observation of dendritic structures is very surprising since hBN was found to grow in compact, triangular-shaped islands on many other metal substrates, in particular, on transition metal surfaces where it shows a much stronger interaction to the surface. We explain the unexpected dendritic growth by an asymmetry of the bonding energy for the two possible ways a borazine molecule can attach to an existing hBN island, namely either with one of its boron or one of its nitrogen atoms. We suggest that this asymmetry originates from different dehydrogenation states of the adsorbed borazine molecules and the hBN islands. We call this mechanism ‘Dehydrogenation Limited Aggregation’ since it is generic in the sense that it is merely based on different dehydrogenation energies for the involved building blocks forming the 2D layer.

Photo electron emission microscopy (PEEM), going back to the earliest days of electron microscopy, and low-energy electron microscopy (LEEM), successfully deployed since the late 1980s, are examples of cathode lens microscopy in which the sample itself is an integral part of the image forming system. While applications have naturally gravitated towards the acquisition of images to elucidate structure and structural evolution, recent years have also seen a rapidly expanding range of spectroscopic capabilities. These address, for example, the occupied and unoccupied electronic band structures of materials, electrical transport in 2-D systems, crystal growth and 2-D strain, inelastic electron energy loss mechanisms, as well as radiation damage in organic materials during low-energy electron irradiation. In this chapter, we discuss applications of these new spectroscopic methods, as well as recent instrumental developments that further expand the potential uses of cathode lens microscopy.

Micro-low energy electron diffraction (μLEED) is frequently used in conjunction with low energy electron microscopy (LEEM) to learn about local surface structural features in small selected areas. Scanning μLEED measurements performed with a very small electron beam (250 nm) can provide precise quantitative information about structural variations with high spatial resolution. We have developed the Source Extraction and Photometry (SEP) – Spot Profile Analysis (SPA) tool for evaluating scanning μLEED data with high throughput. The capability to automate diffraction peak identification with SEP-SPA opens up the possibility to investigate systems with complex diffraction patterns in which diffraction peak positions vary rapidly for small lateral displacements on the surface. The application of this tool to evaluate scanning μLEED data obtained for defective graphene on Cu(111) demonstrates its capabilities. A rich rotational domain structure is observed in which a majority of the graphene is co-aligned with the Cu(111) substrate and the significant remainder comprises domains with large rotations and small sizes that are comparable to the small beam size.

A well-ordered surface oxide grown on Fe(110) has been studied using scanning tunneling microscopy (STM), low energy electron diffraction, low energy electron microscopy, and core level photoelectr ...

Nickel carbide and graphene overlayers were grown on Ni(111), which were in situ monitored by near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and low energy electron microscopy. CO adsorption and desorption on the formed carbon-modified Ni(111) surfaces were further investigated by NAP-XPS. We found that the carbidic carbon weakens CO adsorption on Ni, resulting in quick CO desorption around room temperature. A full graphene layer on Ni(111) blocks CO adsorption in 10–6 Torr CO, while CO intercalates the graphene overlayers in 0.1 Torr CO at room temperature. On the graphene/CO/Ni(111) surface, the major part of intercalated CO molecules desorbs extensively around 90 °C from the graphene/Ni interface and the remaining part gets trapped under the graphene even at 200 °C. These results suggest that the surface reactivity of a metal catalyst can be strongly modulated by surface carbon structures.

Low-energy electron microscopy (LEEM) is a powerful tool that can give a deep insight into in-situ growth. It is a technique which uses elastically backscattered electrons to image a crystalline surface with very high lateral resolution down to few nanometers. It was invented by Ernst Bauer in 1962. After a slow start due to the necessary development of ultrahigh vacuum technology and substrate preparation techniques allowing its use on contaminant-free surfaces, nowadays LEEM microscopy has reached lateral resolution below 2 nm. This gives the opportunity to investigate in real-time and in-situ surfaces, interfaces, thin films, nanostructures, magnetic domains, ranging from the submonolayer to the thin-film regime, and processes on surfaces, such as catalysis. In this book chapter, the basic geometry of the microscope and the contrast mechanisms are briefly discussed. The article presents a LEEM in-situ real-time investigation of organic thin films deposited on gold single crystals.

Low energy electron microscopy and photoemission electron microscopy (LEEM/PEEM), as powerful in-situ surface-sensitive electron microscopy, find wide applications in surface physics, chemistry and catalysis. The high reflectivity of incident low-energy electrons (0–100 eV), allows it to image the surface structures in the topmost few atomic layers within less than one second, while the sample can be heated up to 1200 ℃ in real time which is potentially very useful in metallurgy and materials fields. A unique three-prism aberration correction (ac-) LEEM was commissioned successfully in Chongqing University, with a lateral resolution below 2 nm. A multiple gas source in the ac-LEEM system was installed as well, which allowed us to observe chemical reactions of nanoscale mineral powders on metallic substrates. In this paper, the latest results on the applications of this three-prism ac-LEEM on oxidation and reduction processes on copper and iron polycrystalline surfaces are demonstrated.

Multilayer graphene has exhibited distinct electronic properties such as the tunable bandgap for optoelectronic applications. Among all graphene growth techniques, thermal decomposition of SiC is regarded as a promising method for production of device-quality graphene. However, it is still very challenging to grow uniform graphene over a large-area, especially multilayer graphene. One of the main obstacles is the occurrence of step bunching on the SiC surface, which significantly influences the formation process and the uniformity of the multilayer graphene. In this work, we have systematically studied the growth of monolayer and multilayer graphene on off-axis 3CSiC(111). Taking advantage of the synergistic effect of periodic SiC step edges as graphene nucleation sites and the unique thermal decomposition energy of 3CSiC steps, we demonstrate that the step bunching can be fully eliminated during graphene growth and large-area monolayer, bilayer, and four-layer graphene can be controllably obtained on high-quality off-axis 3CSiC(111) surface. The low energy electron microscopy results demonstrate that a uniform four-layer graphene has been grown over areas of tens of square micrometers, which opens the possibility to tune the bandgap for optoelectronic devices. Furthermore, a model for graphene growth along with the step bunching elimination is proposed. Funding agencies: Swedish Research Council (Vetenskapsradet) [621-2014-5461, 621-2014-5825]; Swedish Research Council for Environment, Agricultural Sciences and Spatial Planning (FORMAS) [2016-00559]; Swedish Foundation for International Cooperation in Research and Higher

Graphene is, due to its extraordinary properties, a promising material for future electronic applications. A common process for the production of large area epitaxial graphene is a high temperature annealing process of atomically flat surfaces from hexagonal silicon carbide. This procedure is very promising but has the drawback of the formation of a buffer layer consisting of a graphene-like sheet, which is covalently bound to the substrate. This buffer layer degenerates the properties of the graphene above and needs to be avoided. We are presenting the combination of a high temperature process for the graphene production with a newly developed substrate of (0 0 1)-oriented cubic silicon carbide. This combination is a promising candidate to be able to supply large area homogenous epitaxial graphene on silicon carbide without a buffer layer. We are presenting the new substrate and first samples of epitaxial graphene on them. Results are shown using low energy electron microscopy and diffraction, photoelectron angular distribution and X-ray photoemission spectroscopy. All these measurements indicate the successful growth of a buffer free few layer graphene on a cubic silicon carbide surface. On our large area samples also the epitaxial relationship between the cubic substrate and the hexagonal graphene could be clarified. (C) 2014 Elsevier Ltd. All rights reserved. (Less)

Monochromatic, aberration-corrected, dual-beam low energy electron microscopy (MAD-LEEM) is a novel technique that is directed towards imaging nanostructures and surfaces with sub-nanometer resolution. The technique combines a monochromator, a mirror aberration corrector, an energy filter, and dual beam illumination in a single instrument. The monochromator reduces the energy spread of the illuminating electron beam, which significantly improves spectroscopic and spatial resolution. Simulation results predict that the novel aberration corrector design will eliminate the second rank chromatic and third and fifth order spherical aberrations, thereby improving the resolution into the sub-nanometer regime at landing energies as low as one hundred electron-Volts. The energy filter produces a beam that can extract detailed information about the chemical composition and local electronic states of non-periodic objects such as nanoparticles, interfaces, defects, and macromolecules. The dual flood illumination eliminates charging effects that are generated when a conventional LEEM is used to image insulating specimens. A potential application for MAD-LEEM is in DNA sequencing, which requires high resolution to distinguish the individual bases and high speed to reduce the cost. The MAD-LEEM approach images the DNA with low electron impact energies, which provides nucleobase contrast mechanisms without organometallic labels. Furthermore, the micron-size field of view when combined with imaging on the fly provides long read lengths, thereby reducing the demand on assembling the sequence. Experimental results from bulk specimens with immobilized single-base oligonucleotides demonstrate that base specific contrast is available with reflected, photo-emitted, and Auger electrons. Image contrast simulations of model rectangular features mimicking the individual nucleotides in a DNA strand have been developed to translate measurements of contrast on bulk DNA to the detectability of individual DNA bases in a sequence.

We report on the high temperature chemical vapor deposition of ethylene on Ir(1 0 0) and the resulting development of single and multi-layer graphene films. By employing X-ray photoemission electron spectromicroscopy, low energy electron microscopy and related microprobe methods, we investigate nucleation and growth of graphene as a function of the concentration of the chemisorbed carbon lattice gas. Further, we characterize the morphology and crystal structure of graphene as a function of temperature, revealing subtle changes in bonding occurring upon cooling from growth to room temperature. We also identify conditions to grow multi-layer flakes. Their thickness, unambiguously determined through the analysis of the intensity of the Ir 4f and C 1s emission, is correlated to the electron reflectivity at very low kinetic energy. The effective attenuation length of electrons in few-layer graphene is estimated to be 4.4 and 8.4 A at kinetic energies of 116 and 338 eV, respectively.

The crystallization of amorphous aluminum oxide thin films formed on NiAl(100) has been investigated using in-situ low energy electron microscopy, low energy electron diffraction, and scanning tunneling microscopy. It is found that both the annealing temperature and annealing time play crucial roles in the crystallization process. A critical temperature range of 450°C–500°C exists for the crystallization to occur within a reasonably short annealing time. The initially uniform oxide film first becomes roughened, followed by coalescing into amorphous-like oxide islands; further annealing results in the conversion of the amorphous oxide islands into crystalline oxide stripes. The density of the crystalline oxide stripes increases concomitantly with the decrease in the density of the amorphous oxide islands for annealing at a higher temperature or longer time.

In low-energy electron microscopy (LEEM) we commonly encounter images which, beside amplitude contrast, also show signatures of phase contrast. The images are usually interpreted by following the evolution of the contrast during the experiment, and assigning gray levels to morphological changes. Through reconstruction of the exit wave, two aspects of LEEM can be addressed: (1) the resolution can be improved by exploiting the full information limit of the microscope and (2) electron phase shifts which contribute to the image contrast can be extracted. In this article, linear exit wave reconstruction from a through-focal series of LEEM images is demonstrated. As a model system we utilize a heteromolecular monolayer consisting of the organic molecules 3,4,9,10-perylene tetracarboxylic dianhydride and Cu-II-Phthalocyanine, adsorbed on a Ag(111) surface.

We synthesized twisted bilayer graphene on single crystalline Ni(111) thin films to analyze the statistical twist angle distribution on a large scale. The twisted bilayer graphene was formed by combining two growth methods, namely the catalytic surface reaction of hydrocarbons and carbon segregation from Ni. Low energy electron diffraction (LEED) investigations directly revealed dominant twist angles of 13 degrees, 22 degrees, 38 degrees, and 47 degrees. We show that the angle distribution is closely related to the sizes of Moire superlattices which form at commensurate rotation angles. In addition to the commensurate angles, quasi-periodic Moire structures were also formed in the vicinity of the dominant angles, confirmed by microscopic observations with low energy electron microscopy and scanning tunneling microscopy (STM). The quasi-periodic Moire patterns are presumably caused by insufficient mobility of carbon atoms during the segregation growth while cooling. Micro-LEED studies reveal that the size of single twisted domains is below 400 nm. Atomic-scale characterization by STM indicates that the twisted layer grown by segregation is located underneath the layer grown by surface reaction, i.e. between the Ni surface and the top single-crystal graphene layer. (C) 2014 Elsevier B.V. All rights reserved.

The adoption of graphene in electronics, optoelectronics, and photonics is hindered by the difficulty in obtaining high-quality material on technologically relevant substrates, over wafer-scale sizes, and with metal contamination levels compatible with industrial requirements. To date, the direct growth of graphene on insulating substrates has proved to be challenging, usually requiring metal-catalysts or yielding defective graphene. In this work, a metal-free approach implemented in commercially available reactors to obtain high-quality monolayer graphene on c-plane sapphire substrates via chemical vapor deposition is demonstrated. Low energy electron diffraction, low energy electron microscopy, and scanning tunneling microscopy measurements identify the Al-rich reconstruction (√31×√31) R ± 9° of sapphire to be crucial for obtaining epitaxial graphene. Raman spectroscopy and electrical transport measurements reveal high-quality graphene with mobilities consistently above 2000 cm2 V-1 s-1. The process is scaled up to 4 and 6 in. wafers sizes and metal contamination levels are retrieved to be within the limits for back-end-of-line integration. The growth process introduced here establishes a method for the synthesis of wafer-scale graphene films on a technologically viable basis.

The ionic component of the strong bond in hexagonal boron nitride (hBN) has been grossly disregarded in literature. Precisely this quantity is demonstrated to govern the shape of monolayer hBN islands grown at high temperatures. HBN zigzag edges are charged and energetically less favorable than the neutral armchair edges, in contrast to those of the purely covalent graphene. Nucleation of hBN islands occurs exclusively on either the inner or the outer corners of substrate steps. Taking into account the charge at edges of hBN islands offers a powerful framework to understand the nucleation of the islands and their orientation with respect the founding steps, as well as various equilibrium shapes, including prominently a right-angled trapezoid. BN dimers are identified as basic building blocks for hBN. A surprisingly strong interaction between hBN and the pre-existing steps on the moderately reactive Ir(1 1 1) substrate is uncovered. Localized charges are probably relevant for all 2D-materials lacking inversion symmetry.

We investigated the structure and crystalline quality of monolayer graphene grown by hydrogen and methane chemical vapor deposition (CVD) on polycrystalline Cu foils. Our data show that the high temperature hydrogen pretreatment of the Cu foil has to be performed at a sufficiently high H 2 pressure in order to avoid graphene (g) formation already during the pretreatment, which limits the achievable domain size during subsequent growth in the CH 4 /H 2 mixture. Methane–hydrogen CVD sustains g growth but induces the faceting of the Cu substrate. Characterization by low energy electron microscopy evidenced a staircase Cu substrate morphology of alternating (4 1 0) and (1 0 0) planes interrupted by (n 1 1) type facets. The g flakes cover the staircase shaped support as a coherent layer. The polycrystalline film mostly contains rotational domains that are preferentially, but not strictly, aligned with respect to the stepped support surface. The substrate induced corrugated morphology occurs also underneath large single crystalline flakes and is transferred to suspended membranes, produced by etching the Cu underneath the graphene. Thus, membranes manufactured from g-Cu are non flat. This explains their reported softened elastic response and the formation of so called nanorippled graphene after transfer from the Cu support which deteriorates its electrical conductivity.

Both Ni and Pb intercalation reactions at graphene/Ru(0001) interface were studied by low energy electron microscopy (LEEM) and photoemission electron microscopy (PEEM). It is suggested that the Ni intercalation is dominated by an exchange intercalation mechanism, in which Ni adatoms produce transient atomic-scale defects in the graphene lattice and penetrate through the carbon monolayer. In contrast, the Pb intercalation process needs to be facilitated by the diffusion of Pb atoms through extended defect sites of graphene, such as open edges and domain boundaries. The two contrast intercalation mechanisms originate from the different interaction strength of the intercalated elements with carbon. Different responses of the graphene electronic structure to the Ni and Pb intercalation reactions were observed by PEEM.

The monochromatic, aberration-corrected, dual-beam low energy electron microscope (MAD-LEEM) is a novel instrument aimed at imaging of nanostructures and surfaces at sub-nanometer resolution that includes a monochromator, aberration corrector and dual beam illumination. The monochromator reduces the energy spread of the illuminating electron beam, which significantly improves spectroscopic and spatial resolution. The aberration corrector utilizes an electron mirror with negative aberrations that can be used to compensate the aberrations of the LEEM objective lens for a range of electron energies. Dual flood illumination eliminates charging generated when a conventional LEEM is used to image insulating specimens. MAD-LEEM is designed for the purpose of imaging biological and insulating specimens, which are difficult to image with conventional LEEM, Low-Voltage SEM, and TEM instruments. The MAD-LEEM instrument can also be used as a general purpose LEEM with significantly improved resolution. The low impact energy of the electrons is critical for avoiding beam damage, as high energy electrons with keV kinetic energies used in SEMs and TEMs cause irreversible change to many specimens, in particular biological materials. A potential application for MAD-LEEM is in DNA sequencing, which demands imaging techniques that enable DNA sequencing at high resolution and speed, and at low cost. The key advantages of the MAD-LEEM approach for this application are the low electron impact energies, the long read lengths, and the absence of heavy-atom DNA labeling. Image contrast simulations of the detectability of individual nucleotides in a DNA strand have been developed in order to refine the optics blur and DNA base contrast requirements for this application.

Nano research 6(8), 562 - 570 (2013). doi:10.1007/s12274-013-0331-9, The atomic and electronic structure of graphene synthesized on commercially available cubic-SiC(001)/Si(001) wafers have been studied by low energy electron microscopy (LEEM), scanning tunneling microscopy (STM), low energy electron diffraction (LEED), and angle resolved photoelectron spectroscopy (ARPES). LEEM and STM data prove the wafer-scale continuity and uniform thickness of the graphene overlayer on SiC(001). LEEM, STM and ARPES studies reveal that the graphene overlayer on SiC(001) consists of only a few monolayers with physical properties of quasi-freestanding graphene. Atomically resolved STM and micro-LEED data show that the top graphene layer consists of nanometersized domains with four different lattice orientations connected through the 〈110〉-directed boundaries. ARPES studies reveal the typical electron spectrum of graphene with the Dirac points close to the Fermi level. Thus, the use of technologically relevant SiC(001)/Si(001) wafers for graphene fabrication represents a realistic way of bridging the gap between the outstanding properties of graphene and their applications., Published by Tsinghua Press, [S.l.]

Summary Commercially available graphene samples are examined by Raman spectroscopy and very low energy scanning transmission electron microscopy. Limited lateral resolution of Raman spectroscopy may produce a Raman spectrum corresponding to a single graphene layer even for flakes that can be identified by very low energy electron microscopy as an aggregate of smaller flakes of various thicknesses. In addition to diagnostics of graphene samples at larger dimensions, their electron transmittance can also be measured at very low energies.

Low-energy electron microscopy (LEEM) has been used to study the structure, initial growth orientation, growth progression, and the number of layers of atomically thin hexagonal boron nitride (h-BN) films. The h-BN films are grown on heteroepitaxial Co using chemical vapor deposition (CVD) at low pressure. Our findings from LEEM studies include the growth of monolayer film having two, oppositely oriented, triangular BN domains commensurate with the Co lattice. The growth of h-BN appears to be self-limiting at a monolayer, with thicker domains only appearing in patches, presumably initiated between domain boundaries. Reflectivity measurements of the thicker h-BN films show oscillations resulting from the resonant electron transmission through quantized electronic states of the h-BN films, with the number of minima scaling up with the number of h-BN layers. First principles density functional theory (DFT) calculations show that the positions of oscillations are related to the electronic band structure of h-BN. Open image in new window

A brief overview of hexagonal superstructures with a periodicity of similar to 3 nm formed on Ru(0001) and Ge(111) by graphene or hexagonal boron nitride with a thickness of just a single atomic layer is given. A periodic height corrugation of such layers due to the lattice mismatch with the substrate material is of the order of 0.1 nm. Selected examples of scanning tunneling microscopy (STM) and low energy electron microscopy/diffraction (LEEM/LEED) investigations of BN/Ru(0001), C/Ru(0001), (BN)(x)C-y/Ru(0001) and C/Ge(111) are presented. These systems can act as nanotemplates for metal nanoparticles growth, as well as strongly heterogeneous substrates for molecular adsorption.

The rare-earth metal, ytterbium (Yb), was deposited on graphene grown on Si-face SiC, kept at room temperature. Yb was not found to intercalate, destroy or dope the graphene layer before subsequent heating, unlike alkali metals such as Li and Na. Our photoemission results reveal that heating to 300?C promotes Yb intercalation into the graphene-substrate interface. Real-time low energy electron microscopy (LEEM) measurements indicated intercalation to start at a sample temperature of around 220oC. In the intercalation process, Yb penetrates through the graphene and buffer layer and forms bonds to the silicon in the topmost SiC substrate bilayer, as indicated by the shifted components observed in the C 1s, Si 2p, and Yb 4f spectra. The Yb intercalation decouples the buffer layer from the substrate and transforms it into another graphene layer as manifested by the absence of buffer layer spots in the μ-LEED pattern and the appearance of an additional π band in the ARPES spectra, respectively. Moreover, the observed shift of the Dirac point down from the Fermi level by 1.9 eV indicates electron doping of the graphene layer upon Yb intercalation. The Yb intercalated graphene sample was found to be thermodynamically stable up to temperatures around 700oC.