The structures of physisorbed and chemisorbed formic acid on Si(1 1 1)-7 × 7

The reaction of formic acid on Si(1 1 1)-7 × 7 was investigated using X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and high-resolution electron energy loss spectroscopy (HREELS). The hydroxyl and carbonyl O 1s core levels of chemisorbed formic acid display chemical shifts of 2.4 and 0.2 eV respectively, compared with those of physisorbed molecules. The HREELS spectra of chemisorbed formic acid show the absence of stretching and bending modes of the O-H bond, the appearance of Si-H (2089 cm⁻¹) and the Si-O (680 cm⁻¹) stretching modes and the retained stretching mode of CO at 1703 cm⁻¹. Our results clearly suggest that formic acid dissociates to form monodentate formate species and H-atom on the adatom-rest atom pair of Si(1 1 1)-7 × 7.     

Electronic properties of (3/2 × 3/2)-Na/Cu(1 1 1)

High-resolution electron energy loss spectroscopy was used to study the electronic properties of (3/2 × 3/2)-Na/Cu(1 1 1) at room temperature. Loss spectra showed two-well distinct losses at 114 and 180 meV assigned to not dispersive charge density waves. Mechanisms to explain their existence are proposed. Moreover, the expected 2D plasmon of the Na quantum well state was not observed. The strong influence of the underlying Cu substrate may be responsible for the absence of such mode.     

Surface phonons of clean, hydrogen- and deuterium-terminated Si(0 0 1) surfaces

We present a comprehensive vibrational study of the clean and hydrogen- or deuterium-terminated silicon (0 0 1) surface. The modes related to the clean as well as to the H:Si, D:Si, and 2H:Si, 2D:Si surfaces are studied by means of high resolution electron energy loss spectroscopy (HREELS). We pay special attention to the modification of the phonon modes by the surface treatments and compare the data with reported experimental and theoretical results. The analysis of the relative phonon intensities of the clean, mono- and dihydride surfaces yields the assignment of the modes related to the dimer bonds. The isotopic shifts of vibrons related to the Si-H and Si-D bonds and to the surface phonon are discussed and applied to the characterisation of the surface excitations.     

Ultra-thin Si overlayers on the TiO2 (1 1 0)-(1 × 2) surface: Growth mode and electronic properties

The growth of thin subnanometric silicon films on TiO₂ (1 1 0)-(1 × 2) reconstructed surfaces at room temperature (RT) has been studied in situ by X-ray and ultra-violet photoelectron spectroscopies (XPS and UPS), Auger electron and electron-energy-loss spectroscopies (AES and ELS), quantitative low energy electron diffraction (LEED-IV), and scanning tunneling microscopy (STM). For Si coverage up to one monolayer, a heterogeneous layer is formed. Its composition consists of a mixture of different suboxides SiO_x (1 < x ? 2) on top of a further reduced TiO₂ surface. Upon Si coverage, the characteristic (1 × 2) LEED pattern from the substrate is completely attenuated, indicating absence of long-range order. Annealing the SiO_x overlayer results in the formation of suboxides with different stoichiometry. The LEED pattern recovers the characteristic TiO₂ (1 1 0)-(1 × 2) diagram. LEED I-V curves from both, substrate and overlayer, indicate the formation of nanometric sized SiO_x clusters.     

Electronic properties of self-assembled quantum dots of sodium on Cu(1 1 1) and their interaction with water

The electronic properties of thin films of Na on Cu(1 1 1) and their interaction with water have been investigated at room temperature by high resolution electron energy loss spectroscopy. The first Na layer is characterized by two features tentatively assigned to charge density waves. The second Na layer grows as small islands. The loss spectrum of this layer shows a feature at 3.0 eV identified as a Mie resonance. Increasing alkali coverage, Na islands form a continuous film, as indicated by the appearance of a Na surface plasmon and by the disappearance of the Mie resonance. Water vapour strongly interacts with Na layers as shown by the OH-Na vibration whose frequency shifts from 36 meV to 53 meV as a function of alkali coverage.     

Covalent binding of cyclohexene, 1,3-cyclohexadiene and 1,4-cyclohexadiene on Si(1 1 1)-7 × 7

The adsorption reactions and binding configurations of cyclohexene, 1,3-cyclohexadiene and 1,4-cyclohexadiene on Si(1 1 1)-7 × 7 were studied using high-resolution electron energy loss spectroscopy (HREELS), ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS) and DFT calculation. The covalent attachments of these unsaturated hydrocarbons to Si(1 1 1)-7 × 7 through the formation of Si–C linkages are clearly demonstrated by the observation of the Si–C stretching mode at 450–500 cm⁻¹ in their HREELS spectra. For chemisorbed cyclohexene, the involvement of π_C=C in binding is further supported by the absence of C=C stretching modes and the disappearance of the π_C=C photoemission. The chemisorption of both 1,3-cyclohexadiene and 1,4-cyclohexadiene leads to the formation of cyclohexene-like intermediates through di-σ bonding. The existence of one π_C=C bond in their chemisorbed states is confirmed by the observation of the C=C and (sp²)C---H stretching modes and the UPS and XPS results. DFT calculations show that [4 + 2]-like cycloaddition is thermodynamically preferred for 1,3-cyclohexadiene on Si(1 1 1)-7 × 7, but a [2 + 2]-like reaction mechanism is proposed for the covalent attachment of cyclohexene and 1,4-cyclohexadiene.     

First-principles study of adsorption and diffusion on Ge/Si(0 0 1)-(2 × 8) and Ge/Si(1 0 5)-(1 × 2) surfaces

Using first-principles total-energy calculations, we have investigated the adsorption and diffusion of Si and Ge adatoms on Ge/Si(0 0 1)-(2 × 8) and Ge/Si(1 0 5)-(1 × 2) surfaces. The dimer vacancy lines on Ge/Si(0 0 1)-(2 × 8) and the alternate S_A and rebonded S_B steps on Ge/Si(1 0 5)-(1 × 2) are found to strongly influence the adatom kinetics. On Ge/Si(0 0 1)-(2 × 8) surface, the fast diffusion path is found to be along the dimer vacancy line (DVL), reversing the diffusion anisotropy on Si(0 0 1). Also, there exists a repulsion between the adatom and the DVL, which is expected to increase the adatom density and hence island nucleation rate in between the DVLs. On Ge/Si(1 0 5)-(1 × 2) surface, the overall diffusion barrier of Si(Ge) along direction is relative fast with a barrier of ∼0.83(0.61) eV, despite of the large surface undulation. This indicates that the adatoms can rapidly diffuse up and down the (1 0 5)-faceted Ge hut island. The diffusion is also almost isotropic along [0 1 0] and directions.     

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.     

Formation and stabilization of Fe-induced magic clusters on Si(1 1 1)-(7 × 7) template

We demonstrate the growth of Fe-induced magic clusters on Si(1 1 1)-(7 × 7) template by in situ scanning tunneling microscopy (STM). These clusters form near a dimer row at one side of the half-unit cell (HUC); and with three different equivalent orientations. A cluster model comprising three top layer Si atoms bonded to six Fe atoms at the next layer in the 7 × 7 faulted-half template is proposed. The optimized cluster structure determined by first-principles total-energy calculation shows an inward-shifting of the three center Fe atoms. The clusters and the nearby center-adatoms of the next HUCs appear with a significantly reduced height below bias voltages 0.4 V in high resolution empty-state STM images, suggesting an energy gap opening near the Fermi level at these localized cluster and adatom sites. We explain the stabilization of the clusters on the 7 × 7 template using the gain in electronic energy as the driving force for cluster formation.     

Vacancy charging on Si(1 1 1)-(7 × 7) investigated by density functional theory

The structure and energetics of charged vacancies on Si(1 1 1)-(7 × 7) are investigated using density functional theory calculations supplemented by estimates of ionization entropy. The calculations predict multiple possible charge states for the unfaulted edge vacancy in the adatom layer, although the −2 state is most stable on real Si(1 1 1) surfaces for which the Fermi level lies near the middle of the band gap.     

The growth of epitaxial VN(1 1 1) nanolayer surfaces

Ultrathin films of vanadium nitride (1-20 monolayers = nanolayers) with (1 1 1) orientation have been grown on a Pt(1 1 1) surface by reactive evaporation of vanadium in NH₃ atmosphere. The VN(1 1 1) surfaces have been investigated by X-ray and UV photoelectron spectroscopy, LEED, work function measurements, and ab initio DFT calculations. Nearly stoichiometric, well-ordered VN_0.9 overlayers with their (1 × 1) unit cells rotationally aligned to the high symmetry directions of the Pt substrate have been obtained after annealing the films deposited at 300-500 °C in vacuum. The experimental valence band spectra have been compared to the theoretical density of states for differently terminated VN(1 1 1) surfaces, i.e. V and N terminated surfaces, bare and with chemisorbed hydrogen. The comparison suggests that the VN(1 1 1) nanolayers are terminated by a hexagonal layer of vanadium atoms, possibly covered with some chemisorbed hydrogen (which may originate from the preparation procedure). The VN nanolayer growth on Pt(1 1 1) follows a Stranski-Krastanov layer-plus-island growth mode.     

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.     

SiO adsorption on a p(2 × 2) reconstructed Si(1 0 0) surface

We have investigated the adsorption mechanism of SiO molecule incident on a clean Si(1 0 0) p(2 × 2) reconstructed surface using density functional theory based methods. Stable adsorption geometries of SiO on Si surface, as well as their corresponding activation and adsorption energies are identified. We found that the SiO molecule is adsorbed on the Si(1 0 0) surface with almost no activation energy. An adsorption configuration where the SiO binds on the channel separating the dimer rows, forming a Si-O-Si bridge on the surface, is the energetically most favourable geometry found. A substantial red-shift in the calculated vibrational frequencies of the adsorbed SiO molecule in the bridging configurations is observed. Comparison of adsorption energies shows that SiO adsorption on a Si(1 0 0) surface is energetically less favourable than the comparable O₂ adsorption. However, the role of SiO in the growth of silicon sub-oxides during reactive magnetron plasma deposition is expected to be significant due to the relatively large amount of SiO molecules incident on the deposition surface and its considerable sticking probability. The stable adsorption geometries found here exhibit structural properties similar to the Si/SiO₂ interface and may be used for studying SiO_x growth.     

Dynamics of copper atoms on Si(1 1 1)-7 × 7 surfaces

This study investigated the dynamics of copper atoms adsorbed on Si(1 1 1)-7 × 7 surfaces between 300 K and 623 K using a variable-temperature scanning tunneling microscope (STM). The diffusion behavior of copper clusters containing up to ∼6 atoms into a particular half unit cell of the 7 × 7 reconstructed Si(1 1 1) surface was considered. The movements and the formation of copper clusters were tracked in detail. The activation energies and pre-exponential factors for various diffusion paths were estimated. Finally, the Cu-etching-Si process and the quasi-5 × 5 incommensurated phase of Cu/Si islands were discussed.     

RT growth of acetonitrile and acrylonitrile on Si(0 0 1)-2 × 1 studied by XPS and LEED

In this work we show the adsorption of acetonitrile (CH₃CN) and acrylonitrile (CH₂CHCN) on Si(0 0 1)-2 × 1 at room temperature by increasing the molecular doses. Especially, by means of XPS and LEED data, we stress the action of these molecules on the silicon surface locating the dangling-bonds quasi-saturation within 10 L. The shortage of nitrogen XPS signal and some anomalies in carbon spectra point to an invading action from a traditional X-ray source (Al-K_α line) against chemisorbed molecules. In particular, we think that a long exposure to this radiation could break carbon-silicon bonds changing some adsorption geometries and making desorb molecular fragments.     

(6 × 2) Reconstruction of the Ag/Si(1 1 1) surface at 77 K

The ground state of the Ag/Si(1 1 1)-(3 × 1) has been investigated by low temperature scanning tunneling microscopy (STM) and density-functional theory. The Fourier transform of the STM image reveals a (6 × 2) reconstruction, which is theoretically found to yield a reconstruction with lower energy than the (3 × 1). The most stable (6 × 2) structural model leads to excellent correspondence between experimental and simulated STM images, and reveals a dimerization of the silver atoms in the channels formed by neighbouring honeycomb Si chains.     

Phosphine and tertiarybutylphosphine adsorption on the indium-rich InP (0 0 1)-(2 × 4) surface

Phosphine and tertiarybutylphosphine adsorption on the indium-rich InP (0 0 1)-(2 × 4) surface at 25 °C have been studied by internal reflection infrared spectroscopy, X-ray photoelectron spectroscopy, and low energy electron diffraction. Both molecules form a dative bond to the empty dangling bonds on the In-P heterodimers and the second-layer In-In dimers and vibrate symmetrically at 2319 (2315) and 2285 (2281) cm⁻¹ and asymmetrically at 2339 (2339) and 2327 (2323) cm⁻¹. A fraction of these species dissociate into adsorbed PH₂ with the hydrogen and tertiarybutyl ligands transferring to nearby phosphorus sites. The calculated energy barriers for desorption (<11 kcal/mol) of these molecules is less than that for dissociation (>17 kcal/mol) and explains their low sticking probabilities at elevated temperatures under InP growth conditions.     

Adsorption and reactions of HN3 on Si(1 0 0)-2 × 1: A computational study

We have studied the adsorption and decomposition of HN₃ on Si(1 0 0)-2 × 1 surface using the hybrid density functional B3LYP method and effective core potential basis, LanL2DZ, with Si₁₅H₁₆ as a double dimer surface model for cluster calculations. The result shows that the barriers for the dissociative adsorption of HN₃ forming HN(a) + N₂(g) are quite low by stepwise dissociation processes occurring either on a dimer or across the dimers. The low activation energies are consistent with previous experimental observations that the molecularly adsorbed HN₃(a) can undergo decomposition producing HN(a) at low surface temperatures. On the other hand, the predicted activation energies for the N₃(a) + H(a) formation processes are all relatively higher. These results also explain the absence of the N₃(a) species in HREELS measurements following each annealing experiment. Several selected reaction paths were also confirmed with slab model calculations using an optimization approach coupling the energy and gradient calculations by the slab model with the geometrical optimization using Berny algorithm.In addition, the adsorbate effect was examined for the end-on and side-on molecular configurations. For the side-on adsorption configuration, all possible combinations with 1-4 adsorbates can exist on the four surface Si sites of the double dimers, with adsorption energies lying closely to the multiples of that of a single side-on adsorbate (LM2); i.e., adsorption energies are nearly additive. Interestingly, for the end-on adsorption, only 1 and 2 HN₃ molecules can adsorb on a dimer due to the presence of the negative charges on the remaining Si sites in the neighboring dimer. For the two end-on adsorbates on the same dimer, the total adsorption energy is close to two times that of HN₃(a) or LM1. For the mixed end-on/side-on configurations, only one of each type can co-exist on a single dimer pair (Si₁-Si₂ or Si₃-Si₄) sites with adsorption energy close to the sum of those of one end-on and one side-on adsorbate. Finally, the predicted reaction routes and vibrational frequencies showed good agreement with previous experimental results. The stabilities of many ad-species involved in these reactions with end-on and/or side-on configurations have been predicted together with the transition states connecting those species.     

First principles study of Si(3 3 5)-Au surface

The structural and electronic properties of gold decorated Si(335) surface are studied by means of density-functional calculations. The resulting structural model indicates that the Au atoms substitute some of the Si atoms in the middle of the terrace in the surface layer. Calculated electronic band structure near the Fermi energy features two metallic bands, one coming from the step edge Si atoms and the other one having its origin in hybridization between the Au and neighboring Si atoms in the middle of the terrace. The obtained electronic bands remain in good agreement with photoemission data.     

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.