Interpretation of scanning tunneling microscopy and atomic force microscopy images of 1T-TiS2

The surface of 1T-TiS₂ was examined by scanning tunneling microscopy (STM) and atomic force microscopy (AFM). The STM and AFM images of this compound were interpreted on the basis of the partial electron density ρ(r,E_F) and total electron density ρ(r) of a slab which consists of six (001) 1T-TiS₂ layers. Electronic structure calculations were performed using the ab-initio Hartree–Fock program crystal. It was found that the bright spots in experimental STM images correspond to sulfur atoms at both positive and negative bias voltages. The AFM image showed a periodicity which can be explained by the atomic corrugation at the surface. Structural defects on the surface were also investigated, and their interpretation constitutes experimental proof that only sulfur atoms were detected by scanning probe microscopies.     

From bilayer to monolayer growth: Temperature effects in the growth of Ru on Pt(1 1 1)

At temperatures around 373 K, Ru growth on Pt(1 1 1) proceeds via nucleation and growth of bilayer islands [H.E. Hoster et al., Phys. Chem. Chem. Phys. 3 (2001) 337]. The influence of the deposition temperature on the Ru growth behavior on Pt(1 1 1) was studied by scanning tunneling microscopy (STM) and Auger electron spectroscopy (AES) in the temperature range between 303 and 773 K. The data reveal a distinct change in the growth characteristics, most important the change from the growth of bilayer Ru islands to monolayer islands, at temperatures between 523 and 573 K. Based on AES data and on atomic resolution STM images, these changes are associated with the onset and increasing contribution of surface alloy formation via Pt–Ru exchange and, at T > 673 K, alloy formation in near surface regions. Consequences of these data for the mechanism of bilayer growth and the underlying physical origin are discussed.     

The role of nitrogen in the preferential chromium segregation on the ferritic stainless steel (1 1 1) surface

The temperature dependence on the segregation behavior of the ferritic stainless steel single crystal (1 1 1) surface morphology has been examined by scanning tunneling microscopy (STM), Auger electron spectroscopy (AES), and low energy electron diffraction (LEED). AES clearly showed the surface segregations of chromium and nitrogen upon annealing. Nanoscale triangular chromium nitride clusters were formed around 650 °C and were regularly aligned in a hexagonal configuration. In contrast, for the ferritic stainless steel (1 1 1) surface with low-nitrogen content, chromium and carbon were found to segregate on the surface upon annealing and Auger spectra of carbon displayed the characteristic carbide peak. For the low-nitrogen surface, LEED identified a facetted surface with (2 × 2) superstructure at 650 °C. High-resolution STM identified a chromium carbide film with segregated carbon atoms randomly located on the surface. The facetted (2 × 2) superstructure changed into a (3 × 3) superstructure with no faceting upon annealing at 750 °C. Also, segregated sulfur seems to contribute to the reconstruction or interfacial relaxation between the ferritic stainless steel (1 1 1) substrate and chromium carbide film.     

Photo-induced tunneling spectroscopy of ReS2: Dramatic increase of the quantum efficiency by chemical treatment

In this work we present a systematic study of the local photovoltaic properties of ReS₂, using a scanning tunneling microscope (STM). The tunneling junction of the STM was optically illuminated during the tunneling process. The phase sensitive detected photo-induced tunneling current (PITC) was studied as a function of wavelength and surface topography. In order to improve the performance of ReS₂ solar cells, the samples were treated with NaI/I₂ and EDTA solutions. Relative to the untreated sample, the EDTA-treated samples show an increase in the photo-induced tunneling current by a factor of 8–10 in the whole spectral range, the NaI/I-treated samples by 2–3. Two dimensional mapping of the PITC was performed on an atomic scale and compared to the surface topography.     

Screw dislocation mediated growth of sputtered and laser-ablated YBa2Cu3O7-δ films

By imaging the as-grown surfaces of sputtered and laserablated YBa₂Cu₃O_7– films with scanning tunneling microscopy (STM), we have directly observed spiral-shaped growth terraces which emanate from screw dislocations. The density of screw dislocations was observed to decrease with increasing growth temperature and substrate misorientation. The surface structures observed by STM together with cross-sectional transmission electron microscope (TEM) images provide insights into the mechanisms of crystal growth operative during the formation of YBa₂Cu₃O_7– films grown using these two widespread techniques.     

In situ electrochemical STM study of platinum nanodot arrays on highly oriented pyrolythic graphite prepared by electron beam lithography

Model electrodes consisting of platinum dots with a mean diameter of (30 ± 5) nm and heights of 3–5 nm upon highly oriented pyrolytic graphite (HOPG) were prepared by electron beam lithography and subsequent sputtering. The Pt nanodot arrays were stable during scanning tunnelling microscopy (STM) measurements in air and in sulphuric acid electrolyte, indicating the presence of “anchors”, immobilising the dots on the HOPG surface.Electrochemical STM was used to visualise potential induced Pt, carbon and Pt-influenced carbon corrosion in situ in 0.5 M sulphuric acid under ambient conditions. Potentiostatic hold experiments show that the Pt dots start to disappear at electrode potentials of E > 1.4 V vs. SHE. With increasing time and potential a hole pattern congruent to the original dot pattern appears on the HOPG basal planes. Corrosion and peeling of the HOPG substrate could also be followed in situ.Dissolution of Pt dots appears to be accelerated for potential cycling experiments compared to the potential hold statistics.     

Surface strain-hardening of iron alloys with an intense pulsed electron beam

Results are presented from study of surface strain-hardening and measurements of the structure of carbon (St. 45, U7A, 40Kh) and alloy (R6M5, Kh6VF) steels subjected to surface fusion by pulsed electron beams with the following parameters: electron energy 20–250 keV, pulse duration 5·10^–8–3·10^–4 sec, power density 10⁵–10⁹ W/cm³. It is shown that the microhardness of the surface of most alloys increases by a factor of 1.2–1.7 on quenched specimens and by a factor of 2.5–3.5 on unquenched specimens, depending on the regime. Microhardness increases in the surface layer due to quenching from the liquid state. An increase in electron energy from 40 to 250 keV with a pulse duration of 6·-10^–8 sec leads to a severalfold increase in the thickness of the strengthened layers and to a shift of the microhardness peak from the surface to a depth of 70 m. Here, microhardness reaches 2000 kgf/mm². This is due to an increase in the mean free path of the electrons in the metal and displacement of the energy-release maximum of the bundle deeper into the specimen.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, No. 6, pp. 38–43, June, 1985.     

The origin of inter-dimer-row correlated adsorption for NH3 on Si(0 0 1)

We discuss the interaction between adsorbing ammonia molecules and pre-adsorbed ammonia fragments on the Si(0 0 1) surface, searching for experimental evidence of a H-bonded precursor state predicted by modelling. While correlations along dimer rows have already been identified, these mix substrate-mediated effects due to dimer buckling with ammonia–adsorbate effects. Correlations between fragments on neighbouring dimer rows are not affected by substrate effects (in this system), allowing an analysis of direct ammonia–adsorbate effects. We present an analysis of cross-row correlations in existing high-coverage STM data which shows significant correlations between NH₂ groups on neighbouring dimer rows over a significant range, providing evidence for the H-bonded precursor state with a range of around 10 Å. We discuss implications for the interpretation of STM images of ammonia on Si(0 0 1).     

XPS and STM study of carbon deposits at the surface of platinum (110)

The deposition of carbon due to high temperature ethylene decomposition at Pt(110) was studied by XPS and STM techniques. In the temperature range 700–1400 K no graphite species were observed. Instead, two carbon states were distinguished by XPS. At temperatures 700–850 K chemisorbed carbon layer is formed with BE(C1s) = 284.2 eV, this carbon state reacting readily with both oxygen and hydrogen. At T> 850 K carbon layer with BE(C1s) = 284.6–284.9 eV is formed. Further study showed this carbon species to be stable up to 1150 K and to be inert towards both hydrogen and oxygen up to 1000 K. This state was attributed to diamond-like carbon (DLC). STM study of DLC on Pt(110) revealed the patched pseudo-C-(3 × 1) structure. This reconstruction is believed to account for the DLC formation at platinum (110) surface.     

Oxygen induced facet formation on Rh(2 1 0) surface

Oxygen induced nanometer-scale faceting of the atomically rough Rh(2 1 0) surface has been studied using Auger electron spectroscopy (AES), low energy electron diffraction (LEED), and scanning tunneling microscopy (STM). The Rh(2 1 0) surface completely covered with nanometer-scale facets when annealed at ≥550 K in the presence of oxygen. LEED studies reveal that the pyramidal faceted surface is characterized by three-sided nanoscale pyramids exposing (7 3 1), (7 3 −1) and (1 1 0) faces. A clean faceted surface was prepared through the use of low temperature surface cleaning method using the reaction with H₂ while preserving (“freezing”) the pyramidal facet structure. The resulting clean faceted surface remains stable for T ∼ 600 K and for higher temperatures; the faceted surface irreversibly relaxes to the planar surface. STM measurements confirms the formation of nanopyramids with average pyramid size ranging from 12 to 21 nm depending upon the annealing temperature. The nanopyramidal faceted Rh surface may be used as a potential template for the growth of metallic nanoclusters and for structure sensitive reactions.     

Laser surface alloying of an electroless Ni–P coating with Al-356 substrate

Laser surface alloying of an electroless plating Ni–P coatings on an Al-356 aluminium alloy was carried out using a 1-kW pulsed Nd:YAG laser. The microstructure, chemical composition and phase identification of the alloyed layer were determined using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and X-ray diffractometry (XRD), respectively. It was shown that laser surface treatment produced a relatively smooth, crack-free and hard surface layer. The hardness of the surface significantly increased due to the formation of the uniformly distributed fine Ni–Al intermetallic phases. The corrosion behaviour of the surface alloyed specimens in 3.5% NaCl solution at 23 °C was also determined by electrochemical techniques. The laser-alloyed surface showed an improved corrosion and pitting potential compared to the substrate as well as the plated Ni–P coating.     

Ultra thin V2O3 films grown on oxidized Si(1 1 1)

The growth of V₂O₃(0 0 0 1) has been investigated by scanning tunnelling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). Direct evaporation of vanadium onto the Si(1 1 1)-7 × 7 substrate gives rise to massive surface intermixing and consequent silicide formation. In order to obtain the vanadium oxide with good quality, the 7 × 7 surface was initially partially oxidized which leads to a smooth oxygen–silicon surface layer which in turn prevents a complete vanadium–silicon alloy formation. Finally a vanadium oxide film of V₂O₃ stoichiometry was created. The grown film exposes single crystalline areas of stepped surfaces which appear azimuthally randomly-oriented.     

Point defects along metallic atomic wires on vicinal Si surfaces: Si(5 5 7)–Au and Si(5 5 3)–Au

Point defects on the metallic atomic wires induced by Au adsorbates on vicinal Si surfaces were investigated using scanning tunneling microscopy and spectroscopy (STM and STS). High-resolution STM images revealed that there exist several different types of defects on the Si(5 5 7)–Au surface, which are categorized by their apparent bias-dependent images and compared to the previous report on Si(5 5 3)–Au [Phys. Rev. B (2007) 205325]. The chemical characteristics of these defects were investigated by monitoring them upon the variation of the Au coverage and the adsorption of water molecules. The chemical origins and the tentative atomic structures of the defects are suggested as Si adatoms (and dimers) in different registries, the Au deficiency on terraces, and water molecules adsorbed dissociatively on step edges, respectively. STS measurements disclosed the electronic property of the majority kinds of defects on both Si(5 5 7)–Au and Si(5 5 3)–Au surfaces. In particular, the dominating water-induced defects on both surfaces induce a substantial band gap of about 0.5 eV in clear contrast to Si adatom-type defects. The conduction channels along the metallic step-edge chains thus must be very susceptible to the contamination through the electronic termination by the water adsorption.     

The role of carbon impurities on the Si(0 0 1)-c(4 × 4) surface reconstruction: Theoretical calculations

In this work we employ the state-of-the-art pseudopotential method, within a generalized gradient approximation to the density functional theory, combined with a recently developed method for the calculation of HREELS spectra to study a series of different proposed models for carbon incorporation on the silicon (0 0 1) surface. A fully discussion on the geometry, energetics and specially the comparison between experimental and theoretical STM images and electron energy loss spectra indicate that the Si(1 0 0)-c(4 × 4) is probably induced by Si-C surface dimers, in agreement with recent experimental findings.     

Electrochemical behaviour of gold modified with contaminated TMP amine adlayers studied by STM, CV, EPR

Scanning tunnelling microscopy (STM), cyclic voltammetry (CV) and electron paramagnetic resonance spectroscopy (EPR) were used to investigate the influence of the TMP amine derivative on Au (1 1 1). The STM results show that the gold surface covered by the adlayer of the TMP derivative is easily modified (holes formation) after increasing the bias voltage to 0.5 V. The CV and EPR results show the electrochemical origin of observed STM topography changes. It is suggested that TMP could be oxidized to the nitroxyl TEMPO radical which adsorbs on Au in the form of an oxoammonium cation. Such an oxoammonium cation at the potential of 0.5 V forms a permanent complex of gold and the nitroxyl radical which could be easily desorbed during STM imaging.     

Substrate orientation: A way towards higher quality monolayer graphene growth on 6H-SiC(0 0 0 1)

The influence of substrate orientation on the morphology of graphene growth on 6H-SiC(0 0 0 1) was investigated using low-energy electron and scanning tunneling microscopy (LEEM and STM). Large area monolayer graphene was successfully furnace-grown on these substrates. Larger terrace widths and smaller step heights were obtained on substrates with a smaller mis-orientation from on-axis (0.03°) than on those with a larger (0.25°). Two different types of a carbon atom networks, honeycomb and three-for-six arrangement, were atomically resolved in the graphene monolayer. These findings are of relevance for various potential applications based on graphene-SiC structures.     

Charge transport properties of composites of multiwalled carbon nanotube with metal catalyst and polymer: application to electromagnetic interference shielding

We report charge transport properties such as d.c. conductivity (σ_DC) and its temperature dependence for composites of poly(methyl methacrylate) (PMMA) and multiwalled carbon nanotubes (MWCNTs). The MWCNTs were synthesized through chemical vapor deposition with Fe or Co as catalyst. The MWCNTs were homogeneously dispersed in PMMA matrix through sonication to prepare MWCNT–PMMA composite films. We controlled mass concentration of MWCNTs in the composites, and the thickness of MWCNT–PMMA composite films was 20–400 μm. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Raman spectroscopy were used to study structure and homogeneity of the composites. The σ_DC at room temperature of MWCNT–PMMA composites increased as mass concentration of MWCNTs increased, which followed percolation theory. Electromagnetic interference (EMI) shielding efficiency (SE) of MWCNT–PMMA composites was measured in the frequency range of 50 MHz–3.5 GHz. We observed the increase of EMI SE of MWCNT–PMMA composites with increasing the concentration of MWCNTs.     

Silicon carbide nanocrystals growth on Si(1 0 0) and Si(1 1 1) from a chemisorbed methanol layer

SiC nanocrystals are grown at high temperature on Si(1 0 0) and Si(1 1 1) surfaces starting from a chemisorbed layer of methanol. The decomposition of this layer allows to have a well defined amount of carbon to feed SiC growth. Nanocrystals ranging from 10 nm to 50 nm with density from 100 μm⁻² to 1500 μm⁻² are obtained, and the total volume of produced SiC corresponds to carbon provided by the chemisorbed organic layer. Large differences in nanocrystal size and density, as well as in surface roughness, are observed depending on substrate orientation. The internal structure, crystallinity and epitaxy of nanocrystals grown on Si(1 0 0) are studied using cross-sectional transmission electron microscopy (XTEM), methanol adsorption and surface evolution using scanning tunnelling microscopy (STM). The joint application of XTEM and STM techniques allows a complete characterization of the geometry and chemical composition of these nanostructures.     

Abnormal adsorption behavior of dimethyl disulfide on gold surfaces

Adsorption of dimethyl disulfide (DMDS) on gold colloidal nanoparticle surfaces has been examined to check its binding mechanism. Differently from previous results, DMDS molecules adsorbed on the gold surface at high concentration showed the S–S stretching band at 500 cm⁻¹ in surface-enhanced Raman scattering (SERS) spectra, which indicates the presence of intact adsorption of DMDS molecules. However, it was found that the S–S bond of disulfides was easily cleaved on the gold surface at low concentration. These behaviors were not observed for diethyl disulfide (DEDS) or diphenyl disulfide (DPDS). Our results indicate that DMDS molecules with the shortest alkyl chains on the gold surface can be inserted into self-assembled monolayers (SAMs) without the S–S bond cleavage during self-assembly due to insufficient lateral van der Waals interaction and the low adsorption activity of disulfides, whereas DEDS with longer alkyl chains or DPDS with the weak disulfide bond dissociation energy would not. These unusual DMDS adsorption behaviors were examined by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). We also compared the bonding dissociation energy of the S–S bonds of various disulfides by means of a density functional theory (DFT) calculation.     

Graphitization of carbon nanofibers: visualizing the structural evolution on the nanometer and atomic scales by scanning tunneling microscopy

The structural evolution of carbon nanofibers submitted to high-temperature (1800, 2300, and 2800 °C) heat treatments has been investigated at the nanometric and atomic scales by means of scanning tunneling microscopy (STM). To complement the local STM observations, X-ray diffraction and Raman spectroscopy characterization of the samples were also carried out. On the nanometer scale, the as-grown nanofibers displayed an isotropic platelet morphology that developed into striped arrangements of increasing width at 1800 and 2300 °C, and into large, atomically flat terraces at 2800 °C. On the atomic scale, the starting nanofibers were characterized by tiny (2 nm) crystallites. The crystallites were observed to coalesce at 1800 °C into appreciably larger (3–4 nm) although still defective units. Atomic structures evidencing truly graphitic ordering (i.e. the typical STM triangular pattern with a periodicity of 0.25 nm) started to develop at 2300 °C. At this temperature, a segregation of graphitic domains and highly defective areas was noticed and attributed mainly to the mobility and subsequent aggregation of point defects (atomic vacancies). Long-range atomic-scale order was generally established in the nanofibers heat treated at 2800 °C, where only some incompletely graphitized, fragmentary graphenes were left on the surface. PACS 81.07.-b; 81.40.Ef; 68.37.Ef