Investigation of hydrogen interaction with the Si(1 1 1)-7 × 7 surface by STM with Bi/W tips

The STM technique with a special Bi/W tip was used to study the interaction of hydrogen atoms with the Si(1 1 1)-7 × 7 surface. The reactivity of different room temperature (RT) adsorption sites, such as adatoms (A), rest atoms (R), and corner holes (CH) was investigated. The reactivity of CH sites was found to be ∼2 times less than that of R and A sites. At temperatures higher than RT, hydrogen atoms rearrange among A, R, and CH sites, with increased occupation of R sites (T <  300 °C). Further temperature increase leads to hydrogen desorption, where its surface diffusion plays an active role. We discuss one of the possible desorption mechanisms, with the corner holes surrounded by a high potential barrier. Hydrogen atoms have a higher probability to overcome the desorption barrier rather than diffuse either into or out of the corner hole. The desorption temperature of hydrogen from CH, R, and A sites is about the same, equal to ∼500 °C. Also it is shown that hydrogen adsorption on the CH site causes slight electric charge redistribution over neighbouring adatoms, namely, increases the occupation of electronic states on A sites in the unfaulted halves of the Si(1 1 1)-7 × 7 unit cell. Based on these findings, the indirect method of investigation with conventional W tips was suggested for adsorbate interaction with CH sites.     

Comparison of S, Pt, and Hf adsorption on NiAl(1 1 0)

First-principles periodic slab density-functional theory (DFT) calculations with a plane-wave basis are used to predict the properties of S, Pt, and Hf adsorption on NiAl(1 1 0). Stable adsorption sites are identified, and adsorbate binding energies and structures are predicted. We find that while S adsorbs in a threefold site, the metals prefer to adsorb in the Ni-Ni twofold bridge site. The latter finding is consistent with scanning tunneling microscopy experiments for adsorption of various transition metals on NiAl(1 1 0) by Ho and coworkers. S is predicted to easily diffuse between threefold sites. We find that Pt and Hf both induce significant changes in the local surface structure, changing twofold bridge sites into fourfold coordination sites by drawing next-nearest-neighbor atoms nearly equidistant with the nearest-neighbor atoms. We find Pt favors interaction with Al slightly more than Ni, while Hf shows a particularly strong affinity for Ni compared to Al. We also predict that Hf may diffuse one-dimensionally along Ni rows with a barrier of ≈0.6 eV.     

Adsorption of Pb on NiAl(1 1 0): energetics and structure

The adsorption of Pb onto a NiAl(1 1 0) single crystal surface at 300 K has been studied by Auger electron spectroscopy (AES), Low energy electron diffraction (LEED), molecular beam/surface scattering and single crystal adsorption calorimetry (SCAC). AES indicates a Stranski-Krastanov growth mode, i.e., Pb initially grows on NiAl(1 1 0) two-dimensionally until the first layer completes at 0.89 ML, where a superstructure is observed by LEED, followed by 3D islanding. Measurements of the Pb gas that does not stick indicate that Pb sticks on NiAl(1 1 0) with an initial probability of 0.99. The initial heat of adsorption of Pb on NiAl(1 1 0) is 249 ± 10 kJ/mol. Due to the repulsive interactions between Pb adatoms, the heat of adsorption decreases within the first layer to a value identical to the heat of sublimation of bulk Pb (195 kJ/mol), where it remains at higher coverages. This first application of adsorption calorimetry on such a thick sample (75 μm versus 0.2-8 μm previously) demonstrates that adsorption calorimetry can be extended to a wider range of surfaces, since this thickness can be achieved with nearly any single crystal material by simple mechanical thinning.     

Morphology and defect structure of the CeO2(1 1 1) films grown on Ru(0 0 0 1) as studied by scanning tunneling microscopy

The morphology of ceria films grown on a Ru(0 0 0 1) substrate was studied by scanning tunneling microscopy in combination with low-energy electron diffraction and Auger electron spectroscopy. The preparation conditions were determined for the growth of nm-thick, well-ordered CeO₂(1 1 1) films covering the entire surface. The recipe has been adopted from the one suggested by Mullins et al. [D.R. Mullins, P.V. Radulovic, S.H. Overbury, Surf. Sci. 429 (1999) 186] and modified in that significantly higher oxidation temperatures are required to form atomically flat terraces, up to 500 Å in width, with a low density of the point defects assigned to oxygen vacancies. The terraces often consist of several rotational domains. A circular shape of terraces suggest a large variety of undercoordinated sites at the step edges which preferentially nucleate gold particles deposited onto these films. The results show that reactivity studies over ceria and metal/ceria surfaces should be complemented with STM studies, which provide direct information on the film morphology and surface defects, which are usually considered as active sites for catalysis over ceria.     

Low reactivity of molecular oxygen with Si(1 1 1)-c(2 × 8)

The adsorption of molecular oxygen on the c(2 × 8) reconstruction of quenched Si(1 1 1) surfaces has been studied at the atomic scale using scanning tunneling microscopy (STM) at room temperature (RT). It has been found that clean well reconstructed c(2 × 8) adatoms do not react with O₂ molecules but that a limited oxidation can start where adatom sites arranged in reconstructed structures are present. Comparison between O₂ adsorption on Si(1 1 1)-c(2 × 8) and Si(1 1 1)-7 × 7 reconstructions coexisting on the same quenched silicon surface has been carried out in detail. For each atomic site present on the surface the variation of reacted sites with exposure has been measured. For low O₂ exposures, bright and dark oxygen induced sites appear on the Si(1 1 1)-7 × 7, while Si(1 1 1)-c(2 × 8) does not oxidized at all. At high O₂ exposures, large oxidation areas have spread on the 7 × 7 reconstruction, preferentially on the faulted halves of the unit cell, and smaller oxidation areas induced by topological defects have grown all around clean un-reacted c(2 × 8) regions.     

The chemisorption of pentacene on Si(0 0 1)-2 × 1

Adsorption structures of the pentacene (C₂₂H₁₄) molecule on the clean Si(0 0 1)-2 × 1 surface were investigated by scanning tunneling microscopy (STM) in conjunction with density functional theory calculations and STM image simulations. The pentacene molecules were found to adsorb on four major sites and four minor sites. The adsorption structures of the pentacene molecules at the four major sites were determined by comparison between the experimental and the simulated STM images. Three out of the four theoretically identified adsorption structures are different from the previously proposed adsorption structures. They involve six to eight Si-C covalent chemical bonds. The adsorption energies of the major four structures are calculated to be in the range 67-128 kcal/mol. It was also found that the pentacene molecule hardly hopped on the surface when applying pulse bias voltages on the molecule, but was mostly decomposed.     

Nanowedge island formation on Mo(1 1 0)

The deposition of ultrathin Fe films on the Mo(1 1 0) surface at elevated temperatures results in the formation of distinctive nanowedge islands. The model of island formation presented in this work is based on both experiment and DFT calculations of Fe adatom hopping barriers. Also, a number of classical molecular dynamics simulations were carried out to illustrate fragments of the model. The islands are formed during a transition from a nanostripe morphology at around 2 ML coverage through a Bales-Zangwill type instability. Islands nucleate when the meandering step fronts are sufficiently roughened to produce a substantial overlap between adjacent steps. The islands propagate along the substrate [0 0 1] direction due to anisotropic diffusion/capture processes along the island edges. It was found that the substrate steps limit adatom diffusion and provide heterogeneous nucleation sites, resulting in a higher density of islands on a vicinal surface. As the islands can be several layers thick at their thinnest end, we propose that adatoms entering the islands undertake a so-called “vertical climb” along the sides of the island. This is facilitated by the presence of mismatch-induced dislocations that thread to the sides of the islands and produce local maxima of compressive strain. Dislocation lines also trigger initial nucleation on the surface with 2-3 ML Fe coverage. The sides of the nanowedge islands typically form along low-index crystallographic directions but can also form along dislocation lines or the substrate miscut direction.     

Corner hole adatom stacking fault structure of Bi on Au(1 1 1)

The surface atomic structure of Bi on Au(1 1 1) is studied with scanning tunneling microscopy. At about 0.5 monolayer of Bi, a well-ordered 6 × 6 atomic structure is observed. The structure has three notable features: corner holes, Bi adatoms, and stacking faults, very similar to a semiconductor surface of Si(1 1 1)-7 × 7. Out of 18 Bi surface atoms in a unit cell, six atoms are at hollow sites and are adatoms, and another six atoms are near-bridge sites. The last six atoms surround corner holes and are lower than other surface atoms by about 0.2 Å. A possible atomic model is proposed based on our observation.     

Ethylene dissociation on flat and stepped Ni(1 1 1): A combined STM and DFT study

The dissociative adsorption of ethylene (C₂H₄) on Ni(1 1 1) was studied by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The STM studies reveal that ethylene decomposes exclusively at the step edges at room temperature. However, the step edge sites are poisoned by the reaction products and thus only a small brim of decomposed ethylene is formed. At 500 K decomposition on the (1 1 1) facets leads to a continuous growth of carbidic islands, which nucleate along the step edges.DFT calculations were performed for several intermediate steps in the decomposition of ethylene on both Ni(1 1 1) and the stepped Ni(2 1 1) surface. In general the Ni(2 1 1) surface is found to have a higher reactivity than the Ni(1 1 1) surface. Furthermore, the calculations show that the influence of step edge atoms is very different for the different reaction pathways. In particular the barrier for dissociation is lowered significantly more than the barrier for dehydrogenation, and this is of great importance for the bond-breaking selectivity of Ni surfaces.The influence of step edges was also probed by evaporating Ag onto the Ni(1 1 1) surface. STM shows that the room temperature evaporation leads to a step flow growth of Ag islands, and a subsequent annealing at 800 K causes the Ag atoms to completely wet the step edges of Ni(1 1 1). The blocking of the step edges is shown to prevent all decomposition of ethylene at room temperature, whereas the terrace site decomposition at 500 K is confirmed to be unaffected by the Ag atoms.Finally a high surface area NiAg alloy catalyst supported on MgAl₂O₄ was synthesized and tested in flow reactor measurements. The NiAg catalyst has a much lower activity for ethane hydrogenolysis than a similar Ni catalyst, which can be rationalized by the STM and DFT results.     

Growth of Si nanostructures on Ag(0 0 1)

The first stages of the growth of silicon on Ag(0 0 1) at moderate temperatures start by the formation of a p(3 × 3) superstructure, which continuously evolves with increasing coverage toward a more complex superstructure. In this paper, the atomic arrangement of the p(3 × 3) and of the “complex” superstructure has been investigated using scanning tunnelling microscopy, surface X-ray diffraction and low energy electron diffraction. The atomic model retained for the p(3 × 3) reconstruction consists in four silicon atoms (tetramers) adsorbed near hollow and bridge sites of the top most Ag(0 0 1) surface layer. For higher coverages, i.e., when the “complex” superstructure starts to develop, the silicon overlayer forms periodic stripes, most probably bi-layers, with a graphitic like structure.     

Chemisorption of atomic oxygen on Pd(1 1 1) studied by STM

Atomic oxygen resulting from the dissociation of O₂ on Pd(1 1 1) at low coverage was studied in a variable temperature scanning tunneling microscope (STM) in the range from 30 to 210 K. Oxygen atoms, which typically appear as 30-40 pm deep depressions on Pd(1 1 1), occupy fcc hollow sites and form ordered p(2 × 2) islands upon annealing above 180 K. The mobility of the atoms diminishes rapidly below 180 K, with an approximate diffusion barrier of 0.4-0.5 eV. Oxygen atom pairs produced by thermal dissociation of O₂ at 160 K occupy both fcc and hcp hollow sites. The atoms travel approximately 0.25 nm after dissociation, and the distribution of pairs is strongly influenced by the presence of subsurface impurities within the Pd sample. At much lower temperatures, the STM tip can dissociate oxygen molecules. Dissociation occurs at sample bias voltages exceeding approximately 0.1 V. Following tip-induced dissociation, the product atoms occupy only fcc hollow sites. Oxygen atoms can be manipulated via short range repulsive interactions with the STM tip.     

Core level photoemission and STM characterization of Ta/Si(1 1 1)-7 × 7 interfaces

We present the results of scanning tunneling microscopy (STM) and photoemission spectroscopy (PES) of the Ta/Si(1 1 1)-7 × 7 system after deposition of Ta at substrate temperatures from 300 to 1250 K. The coverage of Ta varied from 0.05 up to 2.5 of a monolayer (ML). STM shows that at 300 K and coverage less than 1 ML, a disordered chemisorbed phase is formed. Deposition on a hot surface (above 500 K) produces round 3D clusters randomly distributed on the surface. Cluster height and their diameter are found to change drastically with annealing temperature and the Ta coverage. Analysis of photoemission data of the Si 2p core levels shows that at room temperature and at coverage ?1 ML core level binding energy shifts and intensity variations of Si surface related components are observed, which clearly indicate that the reaction starts already at 300 K. Shifts in the binding energy, changes of the peak shapes and intensity of the Ta 4f doublet at higher temperatures can be explained by the formation of stable silicide on the surface.     

STM observation of initial growth of Sn atoms on Ge(0 0 1) surface

We have studied initial growth of Sn atoms on Ge(0 0 1) surfaces at room temperature and 80 K by scanning tunneling microscopy. For Sn deposition onto the Ge(0 0 1) substrate at room temperature, the Sn atoms form two kinds of one-dimensional structures composed of ad-dimers with different alignment, in the 〈3 1 0〉 and the 〈1 1 0〉 directions, and epitaxial structures. For Sn deposition onto the substrate at 80 K, the population of the dimer chains aligning in the 〈3 1 0〉 direction increases. The diffusion barrier of the Sn adatom on the substrate kinetically determines the population of the dimer chain. We propose that the diffusion barrier height depends on surface strain induced by the adatom. The two kinds of dimer chains appearing on the Ge(0 0 1) and Si(0 0 1) surfaces with adatoms of the group-IV elements are systematically interpreted in terms of the surface strain.     

Structural properties of Bi-terminated GaAs(0 0 1) surface

Electronic and structural properties of Bi-terminated reconstructions on GaAs(0 0 1) surface have been studied by scanning tunneling microscopy (STM) and synchrotron radiation core-level spectroscopy. A 2-3 monolayer thick Bi-layer was evaporated on a Ga-terminated GaAs(0 0 1) surface. By heating the surface, the reconstruction changed from (2 × 1) to (2 × 4). The α2 phase with one top Bi dimer and one As or Bi dimer in the third atomic layer per surface unit cell is proposed to explain the STM images of the Bi/GaAs(0 0 1)(2 × 4) surface heated at 400 °C. Bi 5d photoemission from the Bi/GaAs(2 × 4) consisted of two components suggesting two different bonding sites for Bi atoms on the (2 × 4) surface. The variation of the surface sensitivity of the photoemission induced no changes in the intensities of the components indicating that the origins of both components lie in the first surface layer.     

Distribution of lattice-strain on partly nitrogen-covered Cu(0 0 1) surfaces

In-plane elastic lattice strain on the Cu(0 0 1)-c(2 × 2)N surfaces is investigated by scanning tunneling microscopy on the surface where nitrogen-adsorbed patches with average size of 5 × 5 nm² (c(2 × 2)N patches) are well separated by wide clean Cu surface. The lattice distortion on clean Cu surface is recognized in the vicinity of the boundary to a c(2 × 2)N patch. The positions of the protrusions observed on the c(2 × 2)N patch are compared with the surrounding undistorted (1 × 1) lattice of the clean Cu surface. Most of the protrusions on the c(2 × 2)N patches locate on the fourfold hollow sites of the undistorted Cu lattice. The lattice distortion is significant only near the boundary to the surrounding clean Cu surface.     

Vanadium nanoclusters on Si(1 1 1) 7 × 7 surface studied by scanning tunneling microscopy

The size distribution and shape transition of self-assembled vanadium silicide clusters on Si(1 1 1) 7 × 7 have been investigated by scanning tunneling microscopy. Nanoclusters were formed by submonolayer vanadium deposition at room temperature followed by subsequent annealing (solid phase epitaxy - SPE). At room temperature, initially V-nanoclusters are formed which occupy sites avoiding the corner hole parts of the unit cells in the Si(1 1 1) 7 × 7 surface. Upon annealing, strong metal-silicon reaction occur leading to the formation of vanadium silicide nanoclusters. As a function of temperature, both, flat (2D) and three dimensional (3D) clusters have been obtained. After annealing at temperatures around 900 K many faceted clusters are created, whereas at higher annealing temperature, around 1300 K, predominantly 3D clusters are formed. The size distribution of SPE grown clusters could be well controlled in the range of 3-10 nm. The cluster size depends on the annealing temperature as well as on the initial vanadium coverage. Based on high resolution STM images a structure model for one kind of vanadium disilicide clusters exposing atomically flat surfaces was proposed.     

Fermi-level dependent morphology in photoinduced bond breaking on (1 1 0) surfaces of III-V semiconductors

The morphology of structural changes of InP(1 1 0)-(1 × 1) and GaAs(1 1 0)-(1 × 1) induced by electronic processes following laser excitation has been studied by scanning tunneling microscopy. Surface-vacancy clusters are predominantly formed on n-type surfaces, while isolated anion monovacancies are generated almost exclusively on p-type surfaces. This remarkable Fermi-level effect in the morphology is characterized in terms of a screened Coulomb type interaction between charged surface monovacancies and carriers generated by laser excitation. It is shown that localization of photogenerated valence holes induces electronic bond rupture at surface sites.     

Oxygen-induced p(3 × 1) reconstruction of the W(1 0 0) surface

The oxidation of the W(1 0 0) surface at elevated temperatures has been studied using room temperature STM and LEED. High exposure of the clean surface to O₂ at 1500 K followed by flash-annealing to 2300 K in UHV results in the formation of a novel p(3 × 1) reconstruction, which is imaged by STM as a missing-row structure on the surface. Upon further annealing in UHV, this surface develops a floreted LEED pattern characteristic of twinned microdomains of monoclinic WO_x, while maintaining the p(3 × 1) missing-row structure. Atomically resolved STM images of this surface show a complex domain structure with single and double W〈0 1 0〉 rows coexisting on the surface in different domains.     

Investigation of 1,1-dichloroethene interacting with the Si(1 1 1)-7 × 7 surface studied by scanning tunneling microscopy

Adsorption of 1,1-dichloroethene (1,1-DCE) at the Si(1 1 1)-7 × 7 surface has been investigated using scanning tunneling microscopy. 1,1-DCE dissociates upon adsorption by breaking one or both CCl bonds. The appearance of reacted adatoms in the 7 × 7 reconstruction is found to vary for both positive and negative sample bias voltages in the range of 0.8 V to 2.5 V. Dissociated Cl atoms bond to adatom sites and appear bright for bias voltages higher than ±1.4 V. The other dissociated species appear dark for bias voltages below ±1.85 V with a preference of 2:1 for bonding to center relative to corner adatom sites. The faulted half unit cell is preferred. It is demonstrated that rest atoms are active in the dissociation of two-thirds of the 1,1-DCE molecules.     

Angular distributions of atoms sputtered from NiAl{1 1 0} and Ni{1 0 0}

Using the laser post-ionization surface analysis technique, I have for the first time studied angular distributions of Ni and Al atoms sputtered from NiAl{1 1 0}. Emission angular distributions from Ni{1 0 0} have also been measured. I have observed preferential emissions of Ni and Al atoms along 〈1 1 1〉 and 〈1 0 0〉crystallographic directions for NiAl{1 1 0} and of Ni atoms along 〈1 1 0〉 and 〈1 0 0〉 directions for Ni{1 0 0}. The observed preferential ejections can be explained in terms of the theory of focusing-collision sequences. Because of the difference in surface binding energy between Al and Ni atoms, preferential ejection angles of Ni atoms are slightly different from those of Al atoms along the 〈1 1 1〉 ejections. For NiAl, the 〈1 1 1〉 preferential ejections were less prominent than the 〈1 0 0〉 preferential ejections and this can be related to the low efficiency of momentum transfer in Ni-Al collision sequences along 〈1 1 1〉 lattice directions. The low efficiency of momentum transfer due to the mass mismatch can also be responsible for the experimental observation that the preferential ejections in the alloy were less prominent than those in the Ni metal.