The influence of substrate temperature on growth of para-sexiphenyl thin films on Ir{111} supported graphene studied by LEEM

The growth of para-sexiphenyl (6P) thin films as a function of substrate temperature on Ir{111} supported graphene flakes has been studied in real-time with Low Energy Electron Microscopy (LEEM). Micro Low Energy Electron Diffraction (μLEED) has been used to determine the structure of the different 6P features formed on the surface. We observe the nucleation and growth of a wetting layer consisting of lying molecules in the initial stages of growth. Graphene defects – wrinkles – are found to be preferential sites for the nucleation of the wetting layer and of the 6P needles that grow on top of the wetting layer in the later stages of deposition. The molecular structure of the wetting layer and needles is found to be similar. As a result, only a limited number of growth directions are observed for the needles. In contrast, on the bare Ir{111} surface 6P molecules assume an upright orientation. The formation of ramified islands is observed on the bare Ir{111} surface at 320 K and 352 K, whereas at 405 K the formation of a continuous layer of upright standing molecules growing in a step flow like manner is observed.     

Nucleation and growth of Si on Pb monolayer covered Si(111) surfaces

With a scanning tunneling microscope (STM), we study the initial stage of nucleation and growth of Si on Pb monolayer covered Si(111) surfaces. The Pb monolayer can work as a good surfactant for growth of smooth Si thin films on the Si(111) substrate. We have found that nucleation of two-dimensional (2D) Pb-covered Si islands occurs only when the substrate temperature is high enough and the Si deposition coverage is above a certain coverage. At low deposition coverages or low substrate temperatures, deposited Si atoms tend to self-assemble into a certain type of Si atomic wires, which are immobile and stable against annealing to ~ 200 °C. The Si atomic wires always appear as a double bright-line structure with a separation of ~ 9 Å between the two lines. After annealing to ~ 200 °C for a period of time, some sections of Si atomic wires may decompose, meanwhile the existing 2D Pb-covered Si islands grow laterally in size. The self-assembly of Si atomic wires indicate that single Si adatoms are mobile at the Pb-covered Si(111) surface even at room temperature. Further study of this system may reveal the detailed atomic mechanism in surfactant-mediated epitaxy.     

The effects of annealing and growth temperature on the morphologies of Bi nanostructures on HOPG

We report on the growth of ultra-thin bismuth (Bi) films on the basal plane of highly ordered pyrolitic graphite (HOPG) substrates; we investigate the morphologies of films grown at room temperature and then annealed at high temperature, and the morphologies of Bi structures grown at high temperature. Films grown at room temperature nucleate flat islands on the HOPG terraces, and 1D nanorods from HOPG step edges, the islands and rods both have heights in the range 1–3 nm. During annealing, the flat islands break up into groups of aligned, ～ 2.5 nm tall rods. For films grown at high temperature, terrace nucleation is almost nonexistent, and 1D structures grow from step edges, with heights up to 30 nm. Finally, we observe rods with distinctively different morphologies corresponding to (110) and (111) orientations, and infer a surface energy driven Bi(110) to Bi(111) orientation transition. We speculate that the dominant mechanism for the reorientation is coalescence.     

Growth,structure, and thermal stability of epitaxial BaTiO3 films on Pt(111)

The growth of epitaxial ultrathin BaTiO₃ films upon rf magnetron sputter deposition on a Pt(111) substrate has been studied by scanning tunnelling microscopy, low-energy electron diffraction, and X-ray photoelectron spectroscopy. The BaTiO₃ films have been characterized from the initial stages of growth up to a film thickness of 4 unit cells. The deposited films develop a long-range order upon annealing at 1050 K in UHV. In the submonolayer regime a wetting layer is formed on Pt(111). Thicker films reveal a Stranski–Krastanov-like structure as observed with STM. By XPS a good agreement of the thin film stoichiometry with BaTiO₃ single crystal data is determined. Due to annealing at 1150 K BaTiO₃ forms large two-dimensional islands on the Pt(111) substrate. Different surface structures develop on the islands depending on the O₂ partial pressure during annealing.     

Graphene on ordered Ni-alloy surfaces formed by metal (Sn,Al) intercalation between graphene/Ni(111)

Deposition and intercalation of Al and Sn on Ni(111) supported graphene is investigated by Auger electron spectroscopy, low energy electron diffraction, and scanning tunneling microscopy. Al intercalates at ~ 200 °C while Sn intercalates at ~ 350 °C, indicating that the intercalation process is element specific. Both Al and Sn alloy with the Ni-substrate at higher annealing temperatures and form ordered alloy surfaces and surface alloys, respectively. Sn forms a (√3 × √3) R30° surface alloy by substituting surface Ni-atoms with Sn and thus the alloy maintains the same good lattice match with graphene as for Ni(111). Both Sn and Al are interacting weakly with graphene and can therefore be used to decouple graphene from the strongly interacting Ni substrate.     

Initial stages of Bi/Ge(111) interface formation: A detailed STM study

We present a detailed scanning tunneling microscopy investigation of ultra-thin Bi films on Ge(111)-c(2 × 8) in the range up to 1.5 ML. During growth at 300 K, the second/third atomic layer of Bi already starts to nucleate before the completion of the first/second layer correspondingly. Laterally isolated first layer Bi atoms, clusters and islands posses no electronic states in the range ~ 0.5 eV above the Fermi level of the substrate. In contrast, metallic electronic properties are found for continuous films when Bi coverage nears 1 ML. Annealing the as-deposited Bi films at 450 K causes lateral redistribution of Bi due to surface diffusion: coarsening of two-dimensional Bi islands with no long range order in the adsorbate layer is observed up to 1 ML; long range ordered (√3 × √3)-Bi/Ge(111) interface plus three-dimensional Bi clusters are obtained for coverages in excess of 1 ML.     

On the origin of the substrate-induced oxidation of Ni/NiO(001) studied by X-ray Photoelectron Spectroscopy and Molecular Dynamics Simulations

Metallic Ni, vapor-deposited on NiO(001) near room temperature, could be gradually oxidised upon annealing between 800 K and 940 K in Ultra High Vacuum (UHV), as evidenced by X-ray Photoelectron Spectroscopy for initial Ni coverage of 1.6, 3.8 and 7.5 equivalent monolayers (ML). The time dependence of the oxidation process was consistent with a diffusion mechanism, supplying oxygen via the NiO crystal to a coalesced particulate deposit and resulting in an oxide shell, which grew over the entire surface and enclosed a shrinking metallic core. Similar to the well known behaviour upon gas phase oxidation, the process was fast within a depth of two atomic layers of Ni, limited by the diffusive supply of oxygen from the substrate. Molecular Dynamics Simulations for 0.06, 0.11 and 0.22 ML of Ni ions deposited on a model NiO(001) substrate indicated the formation of NiO islands via oxygen ions transferred from the surface and near-surface layers of the crystal. A significant atomic concentration of oxygen vacancies of the order of 10 to 20% could be created in each underneath layer, before the next one started donating lattice anions. This suggests a possible explanation for the aforementioned NiO-substrate-induced oxidation of deposited Ni, whereby the formation of oxygen vacancies inside the crystal supplies the necessary oxygen.     

Synthesis of epitaxial graphene on rhodium from 3-pentanone

The synthesis of high quality single layer graphene on rhodium, g/Rh(111), is reported. The graphene layers are grown at 1060 K by low pressure chemical vapor deposition (CVD) using 3-pentanone as a precursor molecule. The presented growth technique shows an easy high quality production method for epitaxial graphene monolayers. The chemical composition and structural properties of such self-assembled monolayers were characterized by X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED). Scanning Tunneling Microscopy (STM) confirms the formation of a 3 nm super cell and a unique surface morphology which establishes the potential of g/Rh(111) as a template for molecules.     

Kinetic Monte Carlo simulation of the growth of metal clusters on regular array of defects on insulator

A Kinetic Monte Carlo simulation of the nucleation and growth of Pd clusters on a nanostructured alumina substrate is presented. The new Monte Carlo simulation program allows to derive the 3D shape of the growing clusters without performing a full all atoms simulation. The simulation shows, like in previous pure 2D simulations, that clusters nucleate exclusively on the defects of the nanostructure in a limited range of substrate temperature. Around 300 K, the clusters have a compact faceted shape and they grow, at not too large coverage, layer by layer. These results are in agreement with previous studies of the nucleation and growth of Pd clusters on an ultrathin alumina film on Ni₃Al (1 1 1).     

Epitaxial growth of La2Zr2O7 buffer layers for YBa2Cu3O7−δ coated conductors on metallic substrates using pulsed laser deposition

In the present work, La₂Zr₂O₇ (LZO) buffer layers were deposited using pulsed laser deposition (PLD) on various metallic substrates including epitaxial pure Ni on a LaAlO₃ (LAO) substrate as well as highly textured Ni–5 at.%W tapes. It is shown that the LZO deposited on pure Ni-buffered LAO exhibits a mixed orientation while LZO on Ni–5 at.%W grows epitaxially. This difference may be explained by the existence of a sulphur superstructure on the surface of Ni–5 at.%W tapes, promoting the epitaxial (0 0 l) nucleation of seed layers. Highly textured YBa₂Cu₃O_7?δ layers were prepared either by using a single buffer layer of LZO or bilayer buffers of CeO₂/LZO on Ni–5 at.%W. The superconducting transition temperature (T_c) increases with the LZO thickness, reaching a value of 90 K with a very narrow transition width (1.5 K) for 240 nm thick LZO layers. Inductive J_c measurements at 77 K in self-field show a value of about 0.96 MA/cm² for the thickest LZO layers, which is comparable to the value observed on standard buffer architectures such as CeO₂/YSZ/Y₂O₃.     

Embedded Co islands on Ge(001)

The adsorption of Cobalt (Co) on Germanium (Ge) (001) surfaces has been studied using scanning tunneling microscopy. Upon annealing at temperatures of 500–550 K well-ordered rectangular shaped embedded islands are formed. Based on our scanning tunneling microscopy data we propose that the elementary building block of these embedded islands consist of six Co atoms arranged in a hexagonal pattern. A statistical analysis reveals that the embedded Co islands exhibit an attractive interaction in a direction perpendicular to the substrate dimer rows and a repulsive interaction in a direction along the substrate dimer rows. The embedded Co islands eventually convert to perfectly straight and micrometers long nanowires upon annealing at temperatures that exceed 700–750 K.     

Graphene on SiC(0001) and SiC(0001̅) surfaces grown via Ni-silicidation reactions

This paper presents the structure and electronic properties of graphene grown on 6H-SiC(0001) and SiC(0001?) surfaces via Ni-silicidation reactions at temperatures around 800 °C. Silicidation reactions take place at temperature higher than 400 °C for Ni(10 ML)/SiC and a single-phase θ-Ni₂Si(0001)-layer grows epitaxially on SiC(0001?) at 500 °C, whereas a mixed phase silicide-layer is formed on the SiC(0001) substrate. Annealing at 800 °C leads to growth of ordered graphite layers on both SiC(0001?) and SiC(0001) surfaces with an areal occupation ratio of ～ 65%, which surround the Ni-silicide islands. High-resolution ion scattering analysis reveals that single- and double-layer of graphite grow on the SiC(0001?) and SiC(0001), respectively. The dispersion curve of the π band for the double-layer graphite (DG) on the Si-face lies about 1 eV above that of the single-layer graphite (SG) on the C-face around the Γ-point. The work functions of the SG/SiC(0001?) and DG/SiC(0001) are derived to be 5.15 ± 0.05 and 4.25 ± 0.05 eV, respectively, which coincide well with the theoretical prediction based on the ab initio calculations. The present results indicate that the electronic states of graphene are influenced by the interaction with supports.     

Single layer gold islands at the interface between a self-assembled monolayer and the Au(111) substrate: A high-resolution STM study

Physical vapor deposition of gold onto a self-assembled monolayer (SAM) of octanethiol on Au(111) has been studied at the molecular level in ultra-high vacuum (UHV) using atomic-resolution scanning tunneling microscopy (STM). A specially prepared SAM with not only the usual etch pits but also co-existing phases and domain boundaries is used for the purpose of studying details of the nucleation process. Etch pits are found to be filled by deposited Au atoms. At the same time, preferential nucleation and growth of gold islands at intersections of different domains, as well as inside the domains of the less dense striped phase, is observed. We find no gold islands within the densely-packed (√3 × √3)R30° phase. High-resolution STM imaging shows that the SAM over the newly formed gold islands adopts the same structure as that in the immediate surroundings.     

Growth and characterization of Au,Ni and Au–Ni nanoclusters on 6H-SiC(0001) carbon nanomesh

The nucleation and thermal stability of Au, Ni, and Au–Ni nanoclusters on 6H-SiC(0001) carbon nanomesh as well as the interaction between Au–Ni bimetallic clusters and reactive gases have been studied by X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). Both Au and Ni atoms grow as three-dimensional (3D) clusters. Annealing the Au/carbon nanomesh surface up to 1150 °C leads to complete desorption of the Au clusters, while interfacial reaction occurs between Ni clusters and the substrate surface when the Ni clusters are subjected to the same annealing process. The nucleation of Au–Ni clusters depends critically on the deposition sequence. Au atoms preferentially nucleate on the existing Ni clusters, leading to the formation of bimetallic clusters with Au enriched on the surface. If the deposition sequence is reversed, a part of Ni atoms nucleate between the Au clusters. The thermal stability of the Au–Ni clusters resembles that of the Ni/carbon nanomesh surface, irrespective of the deposition sequence. XPS characterization reveals that Ni atoms in Au–Ni bimetallic clusters are oxidized upon exposure to 5.0 × 10^? 7 mbar O₂ for 5 min at room temperature while negligible structure change can be detected when the bimetallic clusters are exposed to CO gas under the similar conditions.     

Two-step method preparation of graphene without hydrogen on methanol pretreatment copper substrate by PECVD at low temperature

Plasma enhanced chemical vapor deposition (PECVD) is one effective method to prepare graphene at low temperature in a short time. However, the low temperature in PECVD could not provide substrate a proper state for large area and few layer graphene preparation. Herein, we propose a two-step method to grow graphene on Cu foils. In the first step, in order to acquire a smooth and oxide-free surface state, methanol was used as a reductant to pretreat Cu. In the second step, graphene films were prepared on Cu foils by PECVD using CH₄ as carbon source with H₂-free. Few-layer graphene sheets with diameter about 1 μm under low temperature (700 °C) and at a short time (10 min) on well pretreated Cu foils were successfully gotten. The effect of methanol pretreatment on graphene synthesis and the graphene growth mechanism on Cu substrate by PECVD are analyzed comprehensively.     

The oxidation of Fe(111)

The oxidation of Fe(111) was studied using Auger electron spectroscopy (AES), low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), ion scattering spectroscopy (ISS) and scanning tunnelling microscopy (STM). Oxidation of the crystal was found to be a very fast process, even at 200 K, and the Auger O signal saturation level is reached within ~ 50 × 10^? 6 mbar s. Annealing the oxidised surface at 773 K causes a significant decline in apparent surface oxygen concentration and produces a clear (6 × 6) LEED pattern, whereas after oxidation at ambient temperature no pattern was observed. STM results indicate that the oxygen signal was reduced due to the nucleation of large, but sparsely distributed oxide islands, leaving mainly the smooth (6 × 6) structure between the islands. The reactivity of the (6 × 6) layer towards methanol was investigated using temperature programmed desorption (TPD), which showed mainly decomposition to CO and CO₂, due to the production of formate intermediates on the surface. Interestingly, this removes the (6 × 6) structure by reduction, but it can be reformed from the sink of oxygen present in the large oxide islands simply by annealing at 773 K for a few minutes. The (6 × 6) appears to be a relatively stable, pseudo-oxide phase, that may be useful as a model oxide surface.     

Theoretical understanding of adlayer structure,thermal stability and electronic property of graphene molecules

The geometry of hexafluorotribenzo[a,g,m]coronene with n-carbon alkyl chains [FTBC-Cn (n = 4, 6, 8, 12)] and their supramolecule self-assembly on a highly oriented pyrolytic graphite (HOPG) surface has been optimized by molecular dynamics simulations using COMPASS force field at 0 K, 298 K, 333 K and 353 K. Electronic properties and intermolecular interactions in graphene supramolecule assembly have been studied by the first principle methods based on the density functional theory (DFT). It is indicated that the thermal stability and electronic properties of graphene molecules can be tunable by attaching alkyl chains to a triangular graphene sheet, and changing the length of the alkyl chain, and self-assembling on a certain substrate. The main results are as follows. The geometry and energy gap of the FTBC-Cn single molecule and their supramolecule self-assembly on HOPG are both stable with the changes of the temperature from 0 K to 353 K and the number of carbon atoms on the alkyl chain. The simulation results of geometry, energy gap as well as STM images of graphene supramolecule assembly are in good agreement with the corresponding experimental results in room temperature. Furthermore, the electronic properties of graphene supramolecule assembly at the temperatures of 0 K, 333 K and 353 K are also predicted. When a triangular graphene molecule attached with six alkyl chains, the energy gaps are increased and stabilized at the temperature from 0 K to 353 K. After FTBC-Cn molecule self-assembly on a HOPG substrate, the energy gap is reduced but still stable.     

In-situ surface-sensitive X-ray diffraction study on the influence of iodide over the selective electrochemical etching of Cu3Au (111)

During selective etching (dealloying) surface-sensitive X-ray diffraction employing Synchrotron light has been used to in-situ monitor the potential-controlled formation of Au-rich films on the surface of Cu₃Au (111) in iodide-containing electrolytes. Similar to the case in pure sulfuric acid we observed a sequence of structural transformations starting from a well-prepared pristine surface to a porous film consisting of substrate-oriented Au ligaments. Also stacking-reversed ultrathin Au-rich films and Au islands form as intermediate steps but no passive-like behavior was observed in iodide-containing electrolytes, i.e. the surface quickly developed Au ligaments after reaching the Cu dissolution potential. At low overpotentials comparatively coarse Au islands point to a higher mobility of Au/electrolyte interfaces in iodide-containing solutions. At higher overpotentials and also with higher iodide concentrations an epitaxial Cu-iodide precipitate film showed an orientation relation of CuI (111) || CuAu (111) and two azimuthal domains of < ? 2, 2, 0 > || < ? 2, 2, 0 > and < ? 2, 2, 0 > || < 2, ? 2, 0>. This partially dissolution-inhibiting bulk CuI layer is observed to produce a bimodal pore size instead of usually obtained homogeneous porosity. The X-ray data and supporting ex-situ AFM and SEM images show marked differences in the morphology and connectivity of the forming nanoporous Au layer. Precipitation layers are thus suggested to provide means for controlling the nanoporosity for applications of dealloyed films and surfaces.     

Interface behavior of Mn/PbTe(111) studied by scanning tunneling microscopy and X-ray photoemission spectroscopy

Mn overlayers growth on PbTe(111) have been investigated by using scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS). The strong chemical interactions were found during the formation of Mn/PbTe(111) interface. At the initial deposition of Mn, one part of Mn adatoms substitute Pb atoms on the PbTe(111) surface, forming a (√3 × √3)R30° MnTe phase, and the other part of Mn adatoms, together with the kicked-out Pb atoms, nucleate at the boundaries of the MnTe islands, forming loop islands around the MnTe islands as an intermediate state. Finally, they develop into regular 3D Pb capped Mn islands upon further Mn deposition. For Mn growth on the PbTe surface where Pb atoms are almost completely substituted by Mn, the deposited Mn atoms either cooperate into the 3D Pb capped Mn islands promoting the upright growth of the 3D Pb capped Mn islands, or nucleate and grow on the MnTe superstructure areas. Free Pb layer always floats on the top of surface, indicating that Pb layer has smaller surface energy, and Mn adatoms always exchange the positions with the underneath Pb atoms during the growth.     

Effect of oxygen on the stability of Ag islands on Si(111)-7 × 7

We have used scanning tunneling microscopy to probe the effect of oxygen exposure on an ensemble of Ag islands separated by a Ag wetting layer on Si(111)-7 × 7. Starting from a distribution dominated by islands that are 1 layer high (measured with respect to the wetting layer), coarsening in ultrahigh vacuum at room temperature leads to growth of 2-layer islands at the expense of 1-layer islands, which is expected. If the sample is exposed to oxygen, 3-layer islands are favored, which is unexpected. There is no evidence for oxygen adsorption on top of Ag islands, but there is clear evidence for adsorption in the wetting layer. Several possible explanations are considered.