Electron and lattice structure of ultra thin Ag films on Si(1 1 1) and Si(0 0 1)

We studied the low temperature (T ? 130 K) growth of Ag on Si(0 0 1) and Si(1 1 1) flat surfaces prepared by Si homo epitaxy with the aim to achieve thin metallic films. The band structure and morphology of the Ag overlayers have been investigated by means of XPS, UPS, LEED, STM and STS. Surprisingly a (√3 × √3)R30° LEED structure for Ag films has been observed after deposition of 2-6 ML Ag onto a Si(1 1 1)(√3 × √3)R30°Ag surface at low temperatures. XPS investigations showed that these films are solid, and UPS measurements indicate that they are metallic. However, after closer STM studies we found that these films consists of sharp Ag islands and (√3 × √3)R30°Ag flat terraces in between. On Si(0 0 1) the low-temperature deposition yields an epitaxial growth of Ag on clean Si(0 0 1)-2 × 1 with a twinned Ag(1 1 1) structure at coverage’s as low as 10 ML. Furthermore the conductivity of few monolayer Ag films on Si(1 0 0) surfaces has been studied as a function of temperature (40-300 K).     

Growth of (√3 × √3)-Ag and (1 1 1) oriented Ag islands on Ge/Si(1 1 1) surfaces

We have studied the growth of Ag on Ge/Si(1 1 1) substrates. The Ge/Si(1 1 1) substrates were prepared by depositing one monolayer (ML) of Ge on Si(1 1 1)-(7 × 7) surfaces. Following Ge deposition the reflection high energy electron diffraction (RHEED) pattern changed to a (1 × 1) pattern. Ge as well as Ag deposition was carried out at 550 °C. Ag deposition on Ge/Si(1 1 1) substrates up to 10 ML has shown a prominent (√3 × √3)-R30° RHEED pattern along with a streak structure from Ag(1 1 1) surface. Scanning electron microscopy (SEM) shows the formation of Ag islands along with a large fraction of open area, which presumably has the Ag-induced (√3 × √3)-R30° structure on the Ge/Si(1 1 1) surface. X-ray diffraction (XRD) experiments show the presence of only (1 1 1) peak of Ag indicating epitaxial growth of Ag on Ge/Si(1 1 1) surfaces. The possibility of growing a strain-tuned (tensile to compressive) Ag(1 1 1) layer on Ge/Si(1 1 1) substrates is discussed.     

Structural investigation of the c(√2 × 5√2)R45° surface alloy formed by Ti deposition on Cu(0 0 1)

The alloying process of Ti deposited on Cu(0 0 1) was studied by means of XPS, LEIS, XPD and LEED intensity analysis. With the sample held at 570 K, a linear decrease of the Cu LEIS signal as a function of the amount of Ti deposited is observed in the early stages of deposition until a constant value is reached. At the onset of the plateau a c(√2 × 5√2)R45° LEED pattern starts to be visible. XPD and LEED intensity measurements were performed for the c(√2 × 5√2)R45° phase prepared depositing ca. 1.5 monolayer of Ti. The angle-scanned XPD curves measured for the phase c(√2 × 5√2)R45° reveal that Ti atoms substitute Cu atoms in the fcc lattice of the substrate. The polar XPD curves show that at least the first four layers of the substrate are involved in the alloying process. We found that the (3 1 0) plane of the Cu₄Ti alloy (D1_a type-structure) fits, without significant contraction or expansion of the lattice parameters, the c(√2 × 5√2)R45° structure. The intensity versus energy curves of the diffracted beams were calculated on the basis of this structural model using the tensor LEED method. The results of the LEED intensity analysis provide a further evidence of the formation of a slab of Cu₄Ti(3 1 0) layers.     

Methylthiolate-induced reconstruction of Ag(1 1 1): A medium energy ion scattering study

Medium energy ion scattering (MEIS), using 100 keV H⁺ incident ions, has been used to investigate the structure of the Ag(1 1 1)(√7 × √7)R19° -CH₃S surface phase. The results provide the first direct evidence that this structure does involve substantial reconstruction of the Ag surface layer. The measured absolute scattered ion yields and blocking curves are in generally good agreement with a specific structural model of the surface based on a reconstructed layer containing 3/7 ML Ag atoms, previously suggested on the basis of scanning tunnelling microscopy (STM) and normal incidence X-ray standing wave (NIXSW) studies. However, the MEIS data indicate that any rumpling of the thiolate layer, is small, and probably ?0.2 Å. This value is smaller than the amplitude suggested in the STM and NIXSW studies, but could be entirely consistent with the earlier experimental data.     

Mixed water/OH structures on Pd(1 1 1)

Chemisorbed O and water react on Pd(1 1 1) at low temperatures to form a mixed OH/H₂O layer with a (√3 × √3)R30° registry. Reaction requires at least two water molecules to each O before the (2 × 2)O islands are consumed, the most stable OH/water structure being a (OH + H₂O) layer containing 0.67 ML of oxygen, formed by the reaction 3H₂O + O → 2(H₂O + OH). This structure is stabilised compared to pure water structures, decomposing at 190 K as OH recombines and water desorbs. The (√3 × √3)R30° − (OH + H₂O) phase cannot be formed by O/H reaction and is distinct from the (√3 × √3)R30° structure formed by O/H coadsorption below 200 K. Mixed OH/water structures do not react with coadsorbed H below 190 K on Pd(1 1 1), preventing this phase catalyzing the low temperature H₂/O₂ reaction which only occurs at higher temperatures.     

Experimental deduction of In/Si(1 1 1) 2D phase diagram and ab initio DFT modeling of 2√3 phase

We have carried out adsorption and residual thermal desorption experiments of Indium on Si (1 1 1) 7 × 7 reconstructed surface, in the submonolayer regime, in Ultra High Vacuum (UHV) using in situ probes such as Auger Electron Spectroscopy (AES) and Low Energy Electron Diffraction (LEED). The coverage information from AES and the surface symmetry from LEED is used to draw a 2D phase diagram which characterizes each observed superstructural phases. The different superstructural phases observed are Si(1 1 1)7 × 7-In, Si(1 1 1)√3 × √3R30°-In, Si(1 1 1)4 × 1-In, Si(1 1 1)2√3 × 2√3R30°-In and Si(1 1 1)√7 × √3-In in characteristic temperature and coverage regime. In addition to the 1/3 ML, √3 × √3-In phase, we observe two additional √3 × √3-In phases at around 0.6 and 1 ML. Our careful residual thermal desorption studies yields the Si(1 1 1)2√3 × 2√3R30°-In phase which has infrequently appeared in the literature. We probe theoretically the structure of this phase according to the LEED structure and coverage measured by AES, assuming that the model for Si(1 1 1)2√3 × 2√3R30°-In is very proximal to the well established Si(1 1 1)2√3 × 2√3R30°-Sn phase, using ab initio calculation based on pseudopotentials and Density Functional Theory (DFT) to simulate an STM image of the system. Calculations show the differences in the atomic position and charge distribution in the Si(1 1 1)2√3 × 2√3R30°-In case.     

STM study of acetylene reaction with Si(1 1 1): observation of a carbon-induced Si(1 1 1)√3×√3R30° reconstruction

The first stages of acetylene reaction with the Si(1 1 1)7 × 7 reconstructed surface kept at 600 °C are studied by recording scanning tunneling microscopy (STM) images during substrate exposure at a C₂H₂ pressure of 2 × 10⁻⁴ Pa (2 × 10⁻² mbar). We observed the progressive substitution of the 7 × 7 reconstruction with a carbon induced Si(1 1 1)√3×√3R30° reconstruction characterized by an atomic distance of 0.75 ± 0.02 nm, very close to that of the silicon 7 × 7 adatoms. This means that a carbon enrichment of the silicon outermost layers occurs giving rise to the formation of a Si-C phase different from the √3×√3R30° reconstruction typical of Si terminated hexagonal SiC(0 0 0 1) surface with an atomic distance of 0.53 nm. To explain STM images, we propose a reconstruction model which involves carbon atoms in T₄ and/or S₅ sites, as occurring for B doped Si(1 1 1) surface. Step edges and areas around the silicon surface defects are the first regions involved in the reaction process, which spreads from the upper part of the step edges throughout the terraces. Step edges therefore, progressively flakes and this mechanism leads, for the highest exposures, to the formation of large inlets which makes completely irregular the straight edge typical of the Si(1 1 1)7 × 7 terraces. These observations indicate that there occurs an atomic diffusion like that driving the meandering effect. Finally, the formation of a few crystallites is shown also at the lowest acetylene exposures. This is the first STM experiment showing the possibility to have carbon incorporation in a Si(1 1 1) matrix for higher amounts than expected, at least up to 1/6 of silicon atomic layer.     

Adsorption and reaction of bicyclic hydrocarbons at Pt(1 1 1) and Sn/Pt(1 1 1) surface alloys: trans-decahydronaphthalene (C10H18) and bicyclohexane (C12H22)

Adsorption and desorption of trans-decahydronaphthalene (C₁₀H₁₈) and bicyclohexane (C₁₂H₂₂) can be used to probe important aspects of non-specific dehydrogenation leading to surface carbon accumulation and establish better estimates of activation energies for C-H bond cleavage at Pt-Sn alloys. This chemistry was studied on Pt(1 1 1) and the (2 × 2)-Sn/Pt(1 1 1) and (√3 × √3)R30°-Sn/Pt(1 1 1) surface alloys by using temperature programmed desorption (TPD) mass spectroscopy and Auger electron spectroscopy (AES). These hydrocarbons are reactive on Pt(1 1 1) surfaces and fully dehydrogenate at low coverages to produce H₂ and surface carbon during TPD. At monolayer coverage, 87% of adsorbed C₁₀H₁₈ and 75% C₁₂H₂₂ on Pt(1 1 1) desorb with activation energies of 70 and 75 kJ/mol, respectively. Decomposition of C₁₀H₁₈ is totally inhibited during TPD on these Sn/Pt(1 1 1) alloys and decomposition of C₁₂H₂₂ is reduced to 10% of the monolayer coverage on the (2 × 2)-Sn/Pt(1 1 1) alloy and totally inhibited on the (√3 × √3)R30°-Sn/Pt(1 1 1) alloy. C₁₀H₁₈ and C₁₂H₂₂ are more weakly chemsorbed on these two alloys compared to Pt(1 1 1) and these molecules desorb in narrow peaks characteristic of each surface with activation energies of 65 and 73 kJ/mol on the (2 × 2) alloy and 60 and 70 kJ/mol on the (√3 × √3)R30°-Sn/Pt(1 1 1) alloy, respectively. Alloyed Sn has little influence on the monolayer saturation coverage of these two molecules, and this is decreased only slightly on these two Sn/Pt(1 1 1) alloys. The use of these two probe molecules enables an improved estimate of the activation energy barriers E* to break aliphatic C-H bonds in alkanes on Sn/Pt alloys; E* = 65-73 kJ/mol on the (2 × 2)-Sn/Pt(1 1 1) alloy and E* ? 70 kJ/mol on the (√3 × √3)R30°-Sn/Pt(1 1 1) alloy.     

Comparative investigation of the c(2 × 2)-Si/Cu(0 1 1) and (√3 × √3)R30°-Cu2Si/Cu(1 1 1) surface alloys using DFT

The electronic structure of the c(2 × 2)-Si/Cu(0 1 1) surface alloy has been investigated and compared to the structures seen in the three phases of the (√3 × √3)R30°Cu₂Si/Cu(1 1 1) system, using LCAO-DFT. The weighted surface energy increase between the alloyed Cu(0 1 1) and Cu(1 1 1) surfaces is 126.7 meV/Si atom. This increase in energy for the (0 1 1) system when compared to the (1 1 1) system is assigned to the transition from a hexagonal to a rectangular local bonding environment for the Si ion cores, with the hexagonal environment being energetically more favorable. The Si 3s state is shown to interact covalently with the Cu 4s and 4p states whereas the Si 3p state, and to a lesser extent the Si 3d state, forms a mixture of covalent and metallic bonds with the Cu states. The Cu 4s and 4p states are shown to be altered by approximately the same amount by both the removal of Cu ion cores and the inclusion of Si ion cores during the alloying of the Cu(0 1 1) surface. However, the Cu 3d states in the surface and second layers of the alloy are shown to be more significantly altered during the alloying process by the removal of Cu ion cores from the surface layer rather than by the addition of Si ion cores. This is compared to the behavior of the Cu 3d states in the surface and second layers of the each phase of the (√3 × √3)R30°-Cu₂Si/Cu(1 1 1) alloy and consequently the loss of Cu-Cu periodicity during alloying of the Cu(0 1 1) surface is conjectured as the driving force for changes to the Cu 3d states. The accompanying changes to the Cu 4s and 4p states in both the c(2 × 2)-Si/Cu(0 1 1) and (√3 × √3)R30°-Cu₂Si/Cu(1 1 1) alloys are quantified and compared. The study concludes with a brief quantitative study of changes in the bond order of the Cu-Cu bonds during alloying of both Cu(0 1 1) and Cu(1 1 1) surfaces.     

Structural evolution of sulfur overlayers on Pd(1 1 1)

Low energy ion scattering spectroscopy (LEISS) has been used to characterize the evolution of ordered structures of S on the Pd(1 1 1) surface during annealing. During exposure of the Pd(1 1 1) surface to 0.7 L H₂S at 300 K—conditions that produce the S(√3 × √3)R30 overlayer—the intensity of the Pd LEIS signal decreases and a feature assigned to adsorbed S appears as the adsorbed layer forms. When the surface is held at 300 K after exposure to H₂S is stopped, the LEIS Pd intensity partially recovers and the S signal weakens, presumably as surface S atoms assume their equilibrium positions in the S(√3 × √3)R30 overlayer. Subsequent annealing of the S(√3 × √3)R30 structure at 700 K causes it to convert into a S(√7 × √7)R19 overlayer, whose LEIS spectrum is identical to that of clean Pd(1 1 1). The absence of LEIS evidence for S atoms at the exposed surface of the S(√7 × √7)R19 overlayer is at odds with published models of a mixed Pd-S top layer. Despite the similarity of the LEIS spectra of Pd(1 1 1) and Pd(1 1 1)-S(√7 × √7)R19, their activities for dissociative hydrogen adsorption are very different—the former readily adsorbs hydrogen at 100 K, while the latter does not—suggesting that S exerts its influence on surface chemistry from subsurface locations.     

Electrochemical scanning tunneling microscopy examination of the structures of benzenethiol molecules adsorbed on Au(1 0 0) and Pt(1 0 0) electrodes

In situ electrochemical scanning tunneling microscopy (STM) has been used to examine the structures of benzenethiol adlayers on Au(1 0 0) and Pt(1 0 0) electrodes in 0.1 M HClO₄, revealing the formation of well-ordered adlattices of Au(1 0 0)-(√2 × √5) between 0.2 and 0.9 V and Pt(1 0 0)-(√2 × √2)R45° between 0 and 0.5 V (versus reversible hydrogen electrode), respectively. The coverage of Au(1 0 0)-(√2 × √5) is 0.33, which is identical to those observed for upright alkanethiol admolecules on Au(1 1 1). In comparison, the coverage of Pt(1 0 0)-(√2 × √2)R45° - benzenethiol is 0.5, much higher than those of thiol molecules on gold surfaces. This result suggests that benzenethiol admolecules on Pt(1 0 0) could stand even more upright than those on Au(1 0 0). All benzenethiol admolecules were imaged by the STM as protrusions with equal corrugation heights, suggesting identical molecular registries on Au(1 0 0) and Pt(1 0 0) electrodes, respectively. Modulation of the potential of a benzenethiol-coated Au(1 0 0) electrode resulted in irreversible desorption of admolecules at E ? 0.1 V (vs. reversible hydrogen electrode) and oxidation of admolecules at E ? 0.9 V. In contrast, benzenethiol admolecule was not desorbed from Pt(1 0 0) at potentials as negative as the onset of hydrogen evolution. Raising the potential rendered deposition of more benzenethiol molecules before oxidation of admolecules commenced at E > 0.9 V.     

Water monolayer and multilayer adsorption on Ni(1 1 1)

Water adsorbed on Ni(1 1 1) forms an ordered, hydrogen bonded ice structure with a (2√7 × 2√7)R19° unit cell. The 2√7 wetting structure forms as islands and persists up to saturation of the first layer. Adsorption of a fraction of a monolayer more water into a second layer destroys the 2√7 registry and creates a disordered ice film. Gas adsorption measurements indicate that the wetting layer is completely covered by a second layer of water before thicker multilayer ice forms. As the second layer is completed the film orders to form an incommensurate crystalline ice film with a hexagonal LEED pattern, oriented to the Ni close packed rows. This ordered, incommensurate structure persists as the ice multilayer grows thicker.     

Surface phase transition and electronic structure of c(5√2 × √2)R45°-Pb/Cu(1 0 0)

The c(5√2 × √2)R45°-Pb/Cu(1 0 0) surface phase is investigated by means of angle resolved ultraviolet photoemission and low energy electron diffraction in the temperature range between 300 and 550 K. We identify and characterize a temperature-induced surface phase transition at 440 K from the room temperature c(5√2 × √2) R45° phase to a (√2 × √2)R45° structure with split superstructure spots. The phase transition is fully reversible and takes place before the two-dimensional melting of the structure at 520 K. The electronic structure of the split (√2 × √2)R45° phase is characterized by a metallic free-electron like surface band. This surface band is backfolded with c(5√2 × √2)R45° periodicity phase at room temperature, giving rise to a surface band gap at the Fermi energy. We propose that a gain in electronic energy explains in part the stability of the c(5√2 × √2)R45° phase.     

Observation of a (√3 × √3)-R30° reconstruction on GaN(0 0 0 1) by RHEED and LEED

A new reconstruction of √3 × √3-R30° has been observed on a GaN film grown on a 6H-SiC (0 0 0 1)-√3 × √3 surface using RHEED and LEED experimental techniques. The experimental LEED PF shows that the GaN film is Ga-terminated hexagonal. The surface is a mixture of two structures with a single bilayer height difference between them. One is a √3 × √3-R30° reconstruction with Ga-adatoms occupying the T4 sites. Another is a Ga-terminated 1 × 1 with no extra Ga on top. The area ratio of the √3 × √3 part to the 1 × 1 part is slightly larger than 1. The first principle total energy calculations and Tensor-LEED I-V curves simulations further confirm this structure model.     

STM study of Bi-on-Cu(1 0 0)

Scanning tunneling microscopy (STM) has been used to study the various possible structures of adsorbed Bi on the Cu(1 0 0) surface, after equilibration at a temperature of 520 K. All of the structures previously identified by X-ray diffraction (lattice gas, c(2 × 2), c(9√2 × √2)R45°, and p(10 × 10), in order of increasing Bi-coverage) were found to be present on a single sample produced by diffusing Bi onto the Cu(1 0 0) surface from a 3-d source. By investigating the possible coexistence of various pairs of phases, it was demonstrated that the c(2 × 2) phase transforms to the c(9√2 × √2)R45° phase by a first order transition, whereas the transition from c(9√2 × √2)R45° to p(10 × 10) is continuous. In addition, the structure of surface steps was studied as a function of Bi-coverage. The results showed that the presence of Bi changes the nature of the step-step interactions at the Cu(1 0 0) surface from repulsive to attractive. The attractive step-step interactions transform any small deviations from the nominal (1 0 0) orientation of the Cu substrate into (3 1 0) microfacets. When compared with the known equilibrium crystal shape (ECS) of Bi-saturated Cu, the observed microfaceting may imply that the ECS of Cu-Bi alloys is temperature dependent.     

Two-photon resonance in optical second harmonic generation from quantum well states in ultra-thin Ag films grown on Si(1 1 1) surfaces

We studied optical second harmonic generation (SHG) oscillations during the growth of Ag films on Si(1 1 1) 7 × 7 clean and H-terminated surfaces. In the growth on the 7 × 7 surfaces at room temperature, the second and third peaks of the oscillation shift towards the thinner side with an increase in pump photon energy. Our analysis revealed that these peaks are caused by two-photon resonant transitions from the n = 1 and 2 occupied quantum well states (QWSs) in the Ag film to the Ag/Si interface at 1.9 eV above the Fermi level (E_f). In Ag growth on the hydrogen-terminated surfaces, the SHG oscillation was similar to that on the 7 × 7 surfaces at room temperature. However, the QWS-related peak was suppressed in the growth at 300 °C. This is attributed to an inhibited intrusion of the interface state into the Ag layers.     

Methanethiolate structural phases on Cu{1 1 1} observed using a novel fibre-optic low-energy electron diffraction instrument

We have used a novel fibre-optic low-energy electron diffraction (FO-LEED) instrument, capable of low flux measurements that minimise electron beam damage to surface overlayers, to study methanethiolate (CH₃-S-) structural phases formed on Cu{1 1 1} at temperatures between 110 and 300 K. Three structural phases were seen: a (√3 × √3)R30° phase that forms at 110-140 K; a (4 × 4) phase which was observed transiently at 110 K; and a pseudo-{1 0 0} reconstructed phase which forms at room temperature. We discuss these in the context of previous studies of this system, and demonstrate the ability of the FO-LEED instrument to record high-quality LEED patterns and intensity data from a strongly beam-sensitive surface.     

Sulfidation of a Cu submonolayer at the Au(1 1 1)/electrolyte interface - An in situ STM study

We describe the electrochemical preparation of an ultrathin copper sulfide film on Au(1 1 1) and its structural characterization by in situ STM. The first step, underpotential deposition of a Cu submonolayer from CuSO₄/H₂SO₄ solution, is followed by two electrolyte exchanges for (i) Cu-free (blank) H₂SO₄ solution and (ii) NaOH/Na₂S solution. The well-known (√3 × √3)R30° structure of the upd Cu layer is stable in the blank electrolyte for at least 2 h. After exposure to bisulfide, the Cu layer contracts and forms two-dimensional islands of two distinct ordered surface phases, i.e. a rectangular and, at higher potentials, a hexagonal phase, with Cu-free Au(1 1 1) regions between them, the latter exhibiting the characteristic (√3 × √3)R30°-S adlayer structure. Potential changes lead to a complex phase behaviour including HS⁻ ? S_x oxidation/reduction and, at strongly anodic potentials, dissolution of the Cu adlayer.     

An STM investigation of the interaction and ordering of pentacene molecules on the Ag/Si(1 1 1)-(√3×√3)R30° surface

Scanning tunneling microscopy has been used to study the ordering of pentacene (C₂₂H₁₄) molecules on the Ag/Si(1 1 1)-(√3×√3)R30° surface at room temperature. Two solid phases, S1 and S2, are observed at coverages of ∼0.35 monolayer (ML) and ∼1.0 ML respectively. It is shown that the solid phase S1 has a high-order commensurate lattice, Ag/Si(1 1 1)-(25 × 25)-pentacene, containing 75 molecules. The structure of this phase is determined from STM measurements at very low coverages where it is possible to image both the pentacene molecules and the structure of the Ag/Si(1 1 1) substrate. Two adsorption sites are identified, a three-fold hollow site at the centre of a Ag-trimer (CA-site) and a six-fold hollow site at the centre of the hexagonal arrangement of silver atoms (CB-site). A higher pentacene coverage of ∼1 ML lead to a molecular reorganization and forms a new commensurate structure Ag/Si(1 1 1)-(2 × 3)-pentacene, containing two molecules per unit cell. Because low energy electron diffraction patterns were not obtainable for this system, the structure of this second phase is determined by using the bias voltage as a tunable parameter to “focus” on either the molecular film or on the substrate. In this phase adsorption takes place exclusively on the Ag-trimer (CA) site and the CB-site is lost because of strong lateral molecule-molecule interactions. The role of competition between intermolecular and molecule-substrate interactions and the nature of the adsorption sites in determining the structure of the pentacene layers is discussed.     

Deduction of a three-phase model for the (√3 × √3)R30°-Cu2Si/Cu(1 1 1) surface alloy

The (√3 × √3)R30°-Cu₂Si/Cu(1 1 1) surface alloy that forms during high temperature dosing of silane (SiH₄) on Cu(1 1 1) has been investigated using LCAO-DFT. Simulated STM images have shown that experimental images may be interpreted as a mixed phase system consisting of Si ion cores bound in HCP, FCC and twofold bridge sites with a ratio of 25:25:50 rather than previously proposed models where the Si ion cores were bound in only FCC and HCP sites. The new model is shown to be consistent with previously published NIXSW studies.