Low-energy Electron Diffraction Study Research Articles

High bunch charge low-energy electron streak diffraction

For time-resolved diffraction studies of irreversible structural dynamics upon photoexcitation, there are constraints on the number of perturbation cycles due to thermal effects and accumulated strain, which impact the degree of crystal order and spatial resolution. This problem is exasperated for surface studies that are more prone to disordering and defect formation. Ultrafast electron diffraction studies of these systems, with the conventional stroboscopic pump–probe protocol, require repetitive measurements on well-prepared diffraction samples to acquire and average signals above background in the dynamic range of interest from few tens to hundreds of picoseconds. Here, we present ultrafast streaked low-energy electron diffraction (LEED) that demands, in principle, only a single excitation per nominal data acquisition timeframe. By exploiting the space–time correlation characteristics of the streaking method and high-charge 2 keV electron bunches in the transmission geometry, we demonstrate about one order of magnitude reduction in the accumulated number of the excitation cycles and total electron dose, and 48% decrease in the root mean square error of the model fit residual compared to the conventional time-scanning measurement. We believe that our results demonstrate a viable alternative method with higher sensitivity to that of nanotip-based ultrafast LEED studies relying on a few electrons per a single excitation, to access to all classes of structural dynamics to provide an atomic level view of surface processes.

Bromine Adsorption and Thermal Stability on Rh(111): A Combined XPS, LEED and DFT Study.

This study addresses a fundamental question in surface science: the adsorption of halogens on metal surfaces. Using synchrotron radiation-based high-resolution X-ray photoelectron spectroscopy (XPS), temperature-programmed XPS, low-energy electron diffraction (LEED) and density functional theory (DFT) calculations, we investigated the adsorption and thermal stability of bromine on Rh(111) in detail. The adsorption of elemental bromine on Rh(111) at 170 K was followed in situ by XPS in the Br 3d region, revealing two individual, coverage-dependent species, which we assign to fcc hollow- and bridge-bound atomic bromine. In addition, we find a significant shift in binding energy upon increasing coverage due to adsorbate-adsorbate interactions. Subsequent heating shows a high thermal stability of bromine on Rh(111) up to above 1000 K, indicating strong covalent bonding. To complement the XPS data, LEED was used to study the long-range order of bromine on Rh(111): we observe a (√3×√3)R30° structure for low coverages (≤0.33 ML) and a star-shaped compression structure for higher coverages (0.33-0.43 ML). Combining LEED and DFT calculations, we were able to visualize bromine adsorption on Rh(111) in real space for varying coverages.

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.

Formation of Large-Area Twisted Bilayer Graphene on Ni(111) Film via Ambient Pressure Chemical Vapor Deposition

Due to the destruction of the intrinsic symmetry between the layers, twisted bilayer graphene has the advantages of available interlayer coupling, tunable electronic bandgap, and diverse phonon dispersion features, which offers a unique platform for the advanced electronic devices. The segregation growth of large-area twisted bilayer graphene on Ni(111) film by ambient pressure chemical vapor deposition (APCVD) methods is presented in this paper. The growth kinetics include two main aspects of the catalytic reaction of methane on the Ni surface and the carbon segregation from the Ni bulk. The large-area twisted bilayer graphene (TBG) can be fabricated by controlling carbon segregation for the continuous second layer graphene that is rotated relative to the first layer graphene. Low energy electron diffraction (LEED) studies reveal a dominant twist angle of about 22.7°. The analysis shows that the dominant twist angle is closely related to the stable energy structure of TBG with the smallest moiré periodicity. Besides, the other twist angles of TBG are also formed in vicinity of the dominant angle, confirmed by microscopic observations with selected area electron diffraction (SAED). The work in this paper provides a convenient route for the synthesis of TBG on Ni(111) substrate, which can promote the application of twisted graphene in future photoelectric and spintronic devices.

Microscopic Study of the Spinodal Decomposition of Supported Eutectic Droplets During Cooling: PtGe/Ge{110}.

We embarked on an in situ low-energy electron microscopy, photo-electron emission microscopy, and selected area low-energy electron diffraction study during the cooling of huge eutectic droplets through the critical stages of the eutectic transition. On this journey through uncharted waters, we revealed an expected initial shrinking of the exposed area of the droplet, followed by an unanticipated expansion. We attribute this behavior to an initial fast amorphization of the interface between the droplet and surface, followed by the recrystallization of Ge expelled from the droplet at the interface. As a major surprise, we discovered the emergence of extensive “spaghetti”-like patterns, which are rationalized in terms of parallel Ge ripples oriented along, mainly, [−554] and [−55–4] directions. They emerge during spinodal decomposition when passing the eutectic temperature of the system. Their sides are defined by Ge{111} and Ge{11–1} vicinals covered with Pt-modified (√3 × √3) superstructures. The distance between adjacent ripples is about 18 nm.

Structure and registry of the silica bilayer film on Ru(0001) as viewed by LEED and DFT.

Silica bilayers are stable on various metal substrates, including Ru(0001) that is used for the present study. In a systematic attempt to elucidate the detailed structure of the silica bilayer film and its registry to the metal substrate, we performed a low energy electron diffraction (I/V-LEED) study. The experimental work is accompanied by detailed calculations on the stability, orientation and dynamic properties of the bilayer at room temperature. It was determined, that the film shows a certain structural diversity within the unit cell of the metal substrate, which depends on the oxygen content at the metal-bilayer interface. In connection with the experimental I/V-LEED study, it became apparent, that a high-quality structure determination is only possible if several structural motifs are taken into account by superimposing bilayer structures with varying registry to the oxygen covered substrate. This result is conceptually in line with the recently observed statistical registry in layered 2D-compound materials.

Insensitivity of the striped charge orders in IrTe2 to alkali surface doping implies their structural origin

We present a combined angle-resolved photoemission spectroscopy and low-energy electron diffraction (LEED) study of the prominent transition metal dichalcogenide IrTe$_2$ upon potassium (K) deposition on its surface. Pristine IrTe$_2$ undergoes a series of charge-ordered phase transitions below room temperature that are characterized by the formation of stripes of Ir dimers of different periodicities. Supported by density functional theory calculations, we first show that the K atoms dope the topmost IrTe$_2$ layer with electrons, therefore strongly decreasing the work function and shifting only the electronic surface states towards higher binding energy. We then follow the evolution of its electronic structure as a function of temperature across the charge-ordered phase transitions and observe that their critical temperatures are unchanged for K coverages of $0.13$ and $0.21$~monolayer (ML). Using LEED, we also confirm that the periodicity of the related stripe phases is unaffected by the K doping. We surmise that the charge-ordered phase transitions of IrTe$_2$ are robust against electron surface doping, because of its metallic nature at all temperatures, and due to the importance of structural effects in stabilizing charge order in IrTe$_2$.

Intercalation of germanium oxide beneath large-area and high-quality epitaxial graphene on Ir(111) substrate* *Project supported by the National Key Research & Development Program of China (Grant Nos. 2019YFA0308500, 2016YFA0202300, and 2018YFA0305800), the National Natural Science Foundation of China (Grant Nos. 61888102, 61925111, and 21661132006), the Strategic Priority Research Program of Chinese Academy of Sciences (Grant Nos. XDB30000000 and XDB28000000), and

Epitaxial growth on transition metal surfaces is an effective way to prepare large-area and high-quality graphene. However, the strong interaction between graphene and metal substrates suppresses the intrinsic excellent properties of graphene and the conductive metal substrates also hinder its applications in electronics. Here we demonstrate the decoupling of graphene from metal substrates by germanium oxide intercalation. Germanium is firstly intercalated into the interface between graphene and Ir(111) substrate. Then oxygen is subsequently intercalated, leading to the formation of a GeO x layer, which is confirmed by x-ray photoelectron spectroscopy. Low-energy electron diffraction and scanning tunneling microscopy studies show intact carbon lattice of graphene after the GeO x intercalation. Raman characterizations reveal that the intercalated layer effectively decouples graphene from the Ir substrate. The transport measurements demonstrate that the GeO x layer can act as a tunneling barrier in the fabricated large-area high-quality vertical graphene/GeO x /Ir heterostructure.

Atomic adsorption of Sn on mechanically cleaved WS2 surface at room temperature

Room temperature (RT) adsorption of tin (Sn) under ultra-high vacuum (UHV) conditions on mechanically cleaved tungsten disulfide (WS2) surfaces is reported here. In-situ low energy electron diffraction (LEED) and scanning tunneling microscopy (STM) studies indicate commensurate adsorption of Sn on the hexagonal surface of WS2. Bare WS2 displays an atomic periodicity of lattice constant 0.34 nm. Growth of Sn reveals monomer like a single atom or unpaired (U) and dimer like- or paired (P) adsorptions on the top (`T’) sulfur (S) sites of the trigonal prismatic sublattice within the honeycomb lattice of WS2. The lateral distance between two nearest adsorbed monomers is around 0.34 nm which is exactly similar to the atomic periodicity of the underneath WS2 substrate crystal. For the case of dimer like- adsorption, the separation between two adspecies is 0.293 nm. The bond length of the adsorbed Sn with the surface S atoms is around 40 (±10) pm. We do not find any evidence of Sn adsorption on the bridge (`B’) or hollow (`H’) site of the WS2 lattice. Analysis of the LEED spots and the FFT images of the STM micrographs after Sn adsorption discloses a stretched hexagonal surface which is most likely due to the overall consequence of a perfectly commensurate monomer and nearly commensurate dimer like- adsorptions of the Sn atoms on the WS2 surface.

2×2R45∘ surface reconstruction and electronic structure of BaSnO3 film

We studied surface and electronic structures of barium stannate (BaSnO$_3$) thin-film by low energy electron diffraction (LEED), and angle-resolved photoemission spectroscopy (ARPES) techniques. BaSnO$_3$/Ba$_{0.96}$La$_{0.04}$SnO$_3$/SrTiO$_3$ (10 nm/100 nm/0.5 mm) samples were grown using pulsed-laser deposition (PLD) method and were \emph{ex-situ} transferred from PLD chamber to ultra-high vacuum (UHV) chambers for annealing, LEED and ARPES studies. UHV annealing starting from 300$^{\circ}$C up to 550$^{\circ}$C, followed by LEED and ARPES measurements show 1$\times$1 surfaces with non-dispersive energy-momentum bands. The 1$\times$1 surface reconstructs into a $\sqrt{2}$$\times$$\sqrt{2}R45^\circ$ one at the annealing temperature of 700$^{\circ}$C where the ARPES data shows clear dispersive bands with valence band maximum located around 3.3 eV below Fermi level. While the $\sqrt{2}$$\times$$\sqrt{2}R45^\circ$ surface reconstruction is stable under further UHV annealing, it is reversed to 1$\times$1 surface by annealing the sample in 400 mTorr oxygen at 600$^{\circ}$C. Another UHV annealing at 600$^{\circ}$C followed by LEED and ARPES measurements, suggests that LEED $\sqrt{2}$$\times$$\sqrt{2}R45^\circ$ surface reconstruction and ARPES dispersive bands are reproduced. Our results provide a better picture of electronic structure of BaSnO$_3$ surface and are suggestive of role of oxygen vacancies in the reversible $\sqrt{2}$$\times$$\sqrt{2}R45^\circ$ surface reconstruction.

(Invited) Growth of Van Der Waals Materials: New Insights from Real-Time Studies

The existence of thousands of new 2D materials has been predicted and several of them have been fabricated, mostly by exfoliation from bulk crystals. In addition to their attractive properties, the availability of these 2D materials also creates a wealth of opportunity to engineer complex van der Waals (vdW) heterostructures, thus laying the groundwork to tailor manipulate the basic properties and device performances. However, despite its numerous advantages, this class of materials is yet to be integrated in real technological applications due to several challenges such as the lack of scalable fabrication processes. With this perspective, quasi-epitaxial growth methods have recently been explored to synthesize 2D materials and vdW heterostructures. Herein, by using group V 2D materials as a model system, this presentation will address the current understanding of vdW growth and the key mechanisms governing the nucleation, growth and stability on weakly interacting surfaces. New insights on the interplay between kinetics and thermodynamic driving forces will be described and discussed based on in situ low-energy electron microscopy and diffraction (LEEM/LEED) studies. The combination of LEEM and LEED with ex situ characterization methods allowed us to elucidate the growth mechanisms of stable and metastable 2D-Sb allotropes and 2D-AsSb alloys on conventional semiconductor substrates and graphene. These results lay the groundwork for the development of scalable vdW epitaxial growth methods for emerging 2D materials and vdW heterostructures.Acknowledgment:The authors acknowledge contributions from Robert Jacobberge, Hannes Zschiesche, Andrea Locatelli, Tevfik O. Menteş, Olga Waller, Charles-Antoine Deslauriers, Francesca Genuzio, Gianluigi Botton, Michael S. Arnold.

Centimeter-Scale and Highly Crystalline Two-Dimensional Alcohol: Evidence for Graphenol (C6OH).

We report a chemical route to synthesize centimeter-scale stoichiometric "graphenol (C6OH1)", a 2D crystalline alcohol, via vapor phase hydroxylation of epitaxial graphene on Cu(111). Atomic resolution scanning tunneling microscopy revealed this highly-ordered configuration of graphenol and low energy electron diffraction studies on a large-area single crystal graphene film demonstrated the feasibility of the same superstructure being achieved at the centimeter length scale. Periodic density functional theory (DFT) calculations about the formation of C6(OH)1 and its electronic structure are also reported.

Electronic structure of Au-Sn compounds grown on Au(111)

The electronic structure of Au-Sn intermetallic layers of different compositions grown on Au(111) to the thickness of several nanometers has been studied in this work. The layer, interface and the substrate related components in the Au 4$f$ and Sn 4$d$ core-level spectra obtained using x-ray photoelectron spectroscopy (XPS) vary with deposition parameters to reveal the details of the Au-Sn formation. While AuSn is grown by deposition at room temperature, Au rich compounds form as a result of heat treatment through inter diffusion of Au and Sn. Deposition at high temperature forms more Au rich compositions compared to post annealing at the same temperature due to the kinetic energy of the impinging Sn atoms in the former case. Post annealing, on the other hand, stabilizes the bulk phases such as AuSn and Au$_5$Sn and exhibits an activated behavior for transition from the former to the latter with increasing temperature. The XPS valence band spectra of AuSn and Au$_{5}$Sn layers show good agreement with the density functional theory calculation, indicating that these have the bulk structure reported in literature. However, the influence of anti-site defects is observed in Au$_5$Sn. Low energy electron diffraction study reveals that although the AuSn layer is ordered, its top surface is disordered at room temperature. Surface order is obtained by annealing or deposition at elevated temperatures and dispersing bands are observed by angle resolved photoemission spectroscopy. Both electron-like and hole-like bands are evident for the ($\sqrt{3}$$\times$$\sqrt{3}$)R30$^{\circ}$ phase, while a nearly free electron-like parabolic surface state is observed for the p(3$\times$3)R15$^{\circ}$ phase.

Atomically Defined Co3O4(111) Thin Films Prepared in Ultrahigh Vacuum: Stability under Electrochemical Conditions

We have explored the stability, the structure, and the chemical transformations of atomically defined Co3O4(111) thin films under electrochemical conditions. The well-ordered Co3O4(111) films were prepared on an Ir(100) single crystal under ultrahigh vacuum (UHV) conditions and subsequently transferred and characterized in the electrochemical environment by means of cyclic voltammetry (CV), scanning flow cell inductively coupled plasma mass spectrometry (SCF-ICP-MS), and electrochemical infrared reflection absorption spectroscopy (EC-IRRAS). We have found that the Co3O4(111) films are stable in phosphate buffer at pH 10 at potentials between 0.33 to 1.33 VRHE. In the corresponding potential range, the corrosion rates established by means of SCF-ICP-MS were well below 0.1 monolayer per hour. Additionally, low-energy electron diffraction (LEED) and X-ray photoelectron spectroscopy (XPS) studies have shown that the long-range order, the thickness, and the composition of the films were preserved under electro...

Surface structure of bulk 2H-MoS2(0001) and exfoliated suspended monolayer MoS2: A selected area low energy electron diffraction study

We have used selected area low energy electron diffraction intensity-voltage (μLEED-IV) analysis to investigate the surface structure of crystalline 2H molybdenum disulfide (MoS2) and mechanically exfoliated and suspended monolayer MoS2. Our results show that the surface structure of bulk 2H-MoS2 is distinct from its bulk and that it has a slightly smaller surface relaxation at 320K than previously reported at 95K. We concluded that suspended monolayer MoS2 shows a large interlayer relaxation compared to the MoS2 sandwich layer terminating the bulk surface. The Debye temperature of MoS2 was concluded to be about 600K, which agrees with a previous theoretical study. Our work has shown that the dynamical μLEED-IV analysis performed with a low energy electron microscope (LEEM) is a powerful technique for determination of the local atomic structures of currently extensively studied two-dimensional (2-D) materials.

Thickness-dependent evolution of structure, electronic structure, and metal-insulator transition in ultrathin V2O3(0001) films on Ag(001)

Epitaxial hexagonal V2O3(0001) films were grown on cubic Ag(001) substrate for coverages ranging from 1-20 monolayers equivalent (MLE) and have studied their structure, electronic structure and the metal-insulator transition (MIT) using Low Energy Electron Diffraction (LEED), X-ray Photoelectron Spectroscopy (XPS) and Angle-Resolved Photoemission Spectroscopy (ARPES) techniques. Detailed LEED and XPS study reveal that, for the lower film coverages (∼1 MLE), a complex (coexisting phase of) vanadium oxide is formed while from 3 MLE coverage onwards, three-dimensional crystallites of V2O3 grows epitaxially. Our LEED results also show that the hexagonal surface of V2O3(0001) is stabilizing on top of square symmetry substrate by the formation of twin-domain structure, where each domain is rotated by 90o. Our photoemission results show that the surface of V2O3 is more insulating than its bulk, similar to the case of many strongly correlated oxide surfaces which is discussed based on the valence band electronic structure with varying probing depth. Evolution of the surface electronic structure was also studied as a function of the film thickness. Further, the effect of lattice strain, film thickness and the domain formation on the metal-insulator transition (MIT) are discussed. The change in the orbital occupancy of (a1g, egπ) and (egπ, egπ) orbitals of V 3 d, a vanishing of quasiparticle (QP) peak and opening an energy gap at the Fermi level is observed below a critical temperature as a consequence of the MIT.

An all-optical electron gun.

Optics Short bunches of electrons are used extensively to yield information about the structure of materials and the dynamics of phase transitions. Traditionally associated, perhaps, with “big science,” the availability of accelerator beam time and the timing resolution of the pulses can be limiting factors for experimental studies. Huang et al. have developed a matchbox-sized all-optical electron gun in which a single terahertz pulse is injected into a copper waveguide. Synchronized with a photogenerated pulse of electrons, the terahertz pulse accelerates the electron bunch over high fields and with low energy spread so that they can be used for low-energy electron diffraction studies. Further developments could lead to the generation of ultrashort relativistic electron bunches and the prospect of miniaturized accelerators. Optica 3 , 1209 (2016).

Single-layer ZnS supported on Au(111): A combined XPS, LEED, STM and DFT study

Single-layer of ZnS, consisting of one atomic layer of ZnS(111) plane, has been grown on Au(111) and characterized using X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). While the LEED measurement indicates a coincidence structure of ZnS-(3×3)/Au(111)-(4×4), high resolution STM images reveal hexagonal unit cells of 6.7×6.7Å2 and 11.6×11.6Å2, corresponding to √3 and 3 times the unit cell of the ideal zincblende ZnS-(1×1), respectively, depending on the tunneling conditions. Calculations based on density functional theory (DFT) indicate a significantly reconstructed non-planar structure of ZnS single-layer on Au(111) with 2/3 of the S anions being located nearly in the plane of the Zn cations and the rest 1/3 of the S anions protruding above the Zn plane. The calculated STM image shows similar characteristics to those of the experimental STM image. Additionally, the DFT calculations reveal the different bonding nature of the S anions in ZnS single-layer supported on Au(111).

Nucleation of Graphene Layers on Magnetic Oxides: Co3O4(111) and Cr2O3(0001) from Theory and Experiment.

We report directly grown strongly adherent graphene on Co3O4(111) by carbon molecular beam epitaxy (C MBE) at 850 K and density functional theory (DFT) findings that the first graphene layer is reconstructed to fit the Co3O4 surface, while subsequent layers retain normal graphene structure. This adherence to the Co3O4 structure results from partial bonding of half the carbons to top oxygens of the substrate. This structure is validated by X-ray photoelectron spectroscopy and low-energy electron diffraction studies, showing layer-by-layer graphene growth with ∼0.08 electrons/carbon atom transferred to the oxide from the first graphene layer, in agreement with DFT. In contrast, for Cr2O3 DFT finds no strong bonding to the surface and C MBE on Cr2O3(0001) yields only graphite formation at 700 K, with C desorption above 800 K. Thus strong graphene-to-oxide charge transfer aids nucleation of graphene on incommensurate oxide substrates and may have implications for spintronics.

CO Adsorption on Reconstructed Ir(100) Surfaces from UHV to mbar Pressure: A LEED, TPD, and PM-IRAS Study.

Clean and stable surface modifications of an iridium (100) single crystal, i.e., the (1 × 1) phase, the (5 × 1) reconstruction, and the oxygen-terminated (2 × 1)-O surface, were prepared and characterized by low energy electron diffraction (LEED), temperature-programmed desorption (TPD), infrared reflection absorption spectroscopy (IRAS) and polarization modulation IRAS (PM-IRAS). The adsorption of CO in UHV and at elevated (mbar) pressure/temperature was followed both ex situ and in situ on all three surface modifications, with a focus on mbar pressures of CO. The Ir(1 × 1) surface exhibited c(4 × 2)/c(2 × 2) and c(6 × 2) CO structures under low pressure conditions, and remained stable up to 100 mbar and 700 K. For the (2 × 1)-O reconstruction CO adsorption induced a structural change from (2 × 1)-O to (1 × 1), as confirmed by LEED, TPD, and IR. For Ir (2 × 1)-O TPD indicated that CO reacted with surface oxygen forming CO2. The (5 × 1) reconstruction featured a reversible and dynamic behavior upon CO adsorption, with a local lifting of the reconstruction to (1 × 1). After CO desorption, the (5 × 1) structure was restored. All three reconstructions exhibited CO adsorption with on-top geometry, as evidenced by IR. With increasing CO exposure the resonances shifted to higher wavenumber, due to adsorbate–adsorbate and adsorbate–substrate interactions. The largest wavenumber shift (from 2057 to 2100 cm–1) was observed for Ir(5 × 1) upon CO dosing from 1 L to 100 mbar.