Atomic and electronic properties of tert-butanol on the Si(001)-(2×1) surface

The atomic and electronic properties of the adsorption of tert-butanol [(CH₃)₃OH] molecule on the Si(001)-(2×1) surface have been studied by using the ab-initio density functional theory (DFT) based on pseudopotential approach. We have found that tert-butanol bonded the Si(001) surface by oxygen atom, cleaving a O–H bond and producing a Si-H bond and tert-butoxy surface species. We have also investigated the influence of chemisorption of tert-butanol on the electronic structure of the clean Si(001)-(2×1) surface. Two occupied surface states situated entirely below the bulk valence band maximum have been identified, which means that the clean Si(001)-(2×1)surface was passivated by the chemisorption of tert-butanol. In order to explain the nature of the surface components we have also plotted the total and partial charge densities at the [`(K)]\bar{K} point of the surface Brillouin zone (SBZ).     

Coverage dependence of glycine adsorption on the Ge(100) − 2 × 1 surface

A combination of infrared spectroscopy, X-ray photoelectron spectroscopy and density functional theory has been used to investigate the adsorption behavior of glycine at the Ge(100) ? 2 × 1 surface under ultrahigh vacuum conditions. Comparison of experimental and simulated IR spectra indicates that at 310 K, glycine adsorbs on Ge(100) ? 2 × 1 via O–H dissociation, with some fraction of the products also forming an N dative bond to a neighboring germanium atom. O–Ge dative bonding is not observed. As coverage increases, the surface concentration of the monodentate O–H dissociated adduct increases, while that of the N dative-bonded species appears constant. XPS data support and clarify the IR findings and reveal new insights, including the presence at higher coverage of a minor product that has undergone dual O–H and N–H dissociation. These findings are supported by the calculated energy diagrams, which indicate that the reaction of a glycine molecule on the Ge(100) ? 2 × 1 surface via O–H dissociation and interdimer N dative bonding is both kinetically and thermodynamically favorable and that N–H dissociation of this adduct is feasible at room temperature given incomplete thermal accommodation along the reaction pathway.     

Bonding geometry of Mn-wires on the Si(100)(2 × 1) surface

The bonding geometry of monoatomic Mn-wires, which form on the reconstructed Si(100)(2 × 1) surface at room temperature, was investigated with scanning tunneling microscopy (STM). The Mn-wire structures are always perpendicular to the Si-dimer rows and the images exhibit a strong modulation of their apparent height as a function of bias voltage. The Mn-wire structures appear as depressions in the empty state images for bias voltages around 0.7 V, and as protrusions for all other bias voltages. It is suggested that the wire-images are defined by mixed Mn-Si states, either through a hybridization between the Mn d-states and the Si-p states, or backbonding from Mn-d electrons into the broken Si-dimer bond. The dominant bonding geometry shows that the Mn-wire maxima are positioned in between the Si-dimer rows, and a small percentage of about 20% is in registry with the Si-dimer rows, and might be described as defective wires. The experimental STM images cannot currently be described in a satisfactory manner with theoretical bonding models from the literature.     

Local electronic structure of the Si(111)-(7 × 7) surface interacting with Ag atoms

Spatially resolved scanning tunneling spectroscopy was used for the investigation of changes in electronic structure of the Si(111)-(7 × 7) surface which are induced by the presence of a silver atom, a dimer and a cluster in a half-unit cell of the surface reconstruction. Tunnel spectra were measured at room temperature at significant positions in half-unit cells. The presence of one or two Ag atoms moving quickly in a half-unit cell significantly influences only filled states in spectra, while empty states remain practically unchanged and are still dominated by silicon adatom states. Corresponding features identified in the filled states depend on the number of Ag atoms in a half-unit cell and localization of these new states reflects the dynamic behavior of the Ag atom in a half-unit cell. A cluster of silver atoms in the half cell exhibits pronounced maxima in both filled and empty states of the spectrum.     

Growth of the Au-induced c(8 × 2) structure on vicinal Ge(001)

We have studied the formation of Ge(001) c(8 × 2)–Au surfaces on vicinal samples by scanning tunneling microscopy. The vicinal samples are tilted 1° toward [110]. The c(8 × 2)–Au surface is prepared by depositing 0.75 ± 0.05 ML of Au onto a germanium surface held at 800 K. The anisotropy introduced by the atomic steps of the vicinal surface and the preferential etching of S_B steps during Au deposition is sufficient to introduce a preferred growth direction for the c(8 × 2)–Au phase. The result is a sample on which 78% of the surface is populated by Au-induced chains oriented parallel to the step direction. These parallel Ge(001) c(8 × 2)–Au domains are separated by single or multiple height D_A steps (0.28 nm high).     

Ga-induced restructuring of Si(5 5 12) − 2 × 1 reconstructed surface at room temperature

Motivated by the need to form 1D-nanostructured dopants on silicon surfaces, we have attempted to grow Ga on the high index Si(5 5 12) surface which has a highly trenched (1D) morphology. The evolution of the interface with Ga adsorption in the monolayer regime has been probed by in situ AES, LEED and EELS. Controlling the kinetics by changing the Ga flux rates shows an interesting difference in the 1.0 to 1.5 ML region. The low flux rate (0.03 ML/minute) results in a Frank van der Merwe (layer by layer) growth mode up to 2 ML, while the higher flux rate (0.1 ML/minute) shows a transient island formation after the completion of 1 ML. The low rate shows the formation of 2 × (3 3 7) and (2 2 5) superstructures, while only the 2 × (3 3 7) is observed in a wide coverage range for the higher rate. The results demonstrate the ability to kinetically control the surface phases with different electronic properties of this technologically important interface.     

Adsorption of small molecules on a (2 × 1) PdZn surface alloy on Pd(1 1 1)

The adsorption of methanol, formaldehyde, methoxy, carbon monoxide and water on a (2 × 1) PdZn surface alloy on Pd(1 1 1) has been studied using DFT calculations. The most stable adsorption structures of all species have been investigated with respect to the structure and the electronic properties. It was found that methanol is only weakly bound to the surface. The adsorption energy only increases with higher methanol coverage, where chain structures with hydrogen bonds between the methanol molecules are formed. The highest adsorption energy was found for the formate species followed by the methoxy species. The formaldehyde species shows quite some electronic interaction with the surface, however the stable η₂ formaldehyde has only an adsorption energy of about 0.49 eV. The calculated IR spectra of the different species fit quite well to the experimental values available in the literature.     

First principles calculations of the Sc adsorption on Si(001)-c(2 × 4)

We have investigated the energetics and the atomic structure of the adsorption of Sc on the Si(001)-c(2 × 4) surface using first principles total energy calculations, within the periodic density functional. The Sc adsorption has been studied at high symmetry sites considering different concentrations. We have first explored the one atom case and then increased the coverage up to a 0.25 of a monolayer of Sc. For the adsorption of one Sc atom we have obtained that the most stable configuration corresponds to the adsorption in the trench between two Si dimers, at the C1 (cave) site. The interaction of the adsorbed Sc with the Si dimers induces a decrease of the dimers buckling amplitude. On the other hand Si dimers without interaction with the adsorbate have buckling amplitudes similar to those of the clean Si surface. When the Sc coverage is increased to two Sc atoms, the most stable structure corresponds to the adsorption at two consecutive V (valley-bridge) sites along the trench between Si dimers, resulting in the weakening of some of the Si dimers bonds. This result indicates that the formation of one dimensional Sc chains on the silicon surface is energetically and kinetically favorable.     

The effect of compositional disorder on electronic band structure in GaxIn1 − xAsySb1 − yalloys lattice matched to GaSb

A pseudopotential formalism coupled with the virtual crystal approximation are applied to study the effect of compositional disorder upon electronic band structure of cubic Ga_xIn_1 − xAs_ySb_1 − yquarternary alloys lattice matched to GaSb. The effects of compositional variations are properly included in the calculations. Our theoretical results show that the compositional disorder plays an important role in the determination of the energy band structure of Ga_xIn_1 − xAs_ySb_1 − y/GaSb and that the bowing parameter is dominated by the group V-anion-based sublattice. Moreover, the absorption at the fundamental optical gaps is found to be direct within a whole range of the x composition.     

Cation-anion mixed-dimer structure of Al-induced (2 × 4) reconstruction on InAs(001)

Adsorption of Al atoms on the As-stabilized InAs(001)—(2 × 4) surface induces the formation of the Al-stabilized (2 × 4) reconstruction. The Al-stabilized (2 × 4) surface has mixed In–As dimer at the outermost layer with the Al atoms being incorporated into the subsurface layers. Heating of the Al-stabilized (2 × 4) surface further promotes the diffusion of Al into deeper layers, which results in the formation of the In-rich (4 × 2) structure with the ζa structure.     

Self-assembled line growth of allyl alcohol on the H-terminated Si(100)-(2 × 1) surface

Using first-principles density-functional calculations, we investigate the growth mechanism of allyl alcohol (ALA) line on the H-terminated Si(100)-(2 × 1) surface. Unlike the allyl mercaptan (CH₂ = CH ? CH₂ ? SH) line, which was observed to grow across the Si dimer rows, we find that ALA (CH₂ = CH ? CH₂ ? OH) has the line growth along the Si dimer row. The self-assembled growth of ALA line occurs via the radical chain reaction mechanism, similar to the case of a typical alkene molecule, styrene. Our calculated energy profile along the reaction pathway shows that the different growth direction of ALA line compared with that of allyl mercaptan line is ascribed to the great instability of the oxygen radical intermediate, which prevents the line growth across the dimer rows.     

Understanding 4-bromostyrene Adsorption on the Si(001)-(1 × 2) surface: A density functional theory study

Adsorption properties of 4-bromostyrene (Br–Sty) on the Si(001)-(1 × 2) surface are investigated by ab initio calculation based on density functional theory (DFT). For the adsorption of Br–Sty molecule on the Si(001)-(1 × 2) surface, we have assumed two possible cases within: (i) binding on the partially H-terminated surface and (ii) binding on the clean surface. For the first case, we have estimated two different binding sides: (i) Bromine-terminated bindings and (ii) Carbon-terminated binding. The adsorption energies of Br-terminated and C-terminated binding were found as 0.36 eV and 3.76 eV, respectively. In the same manner, we have also assumed two possible binding sides for the clean surface: (i) Br-terminated binding and (ii) ring-shaped binding. We have found adsorption energies for Br-terminated and ring-shaped binding as 0.14 eV and 1.10 eV on the clean surface, respectively. Moreover, the nudged elastic band method (NEB) was used to reveal the adsorption pathway of these binding models. These results serve to understand the possibility of the adsorption of Br–Sty molecules onto different kind of silicon surfaces into different reaction conditions.     

Interaction of Ag with the Si(1 1 1)1 × 1–H surface

Synchrotron radiation based photoemission spectroscopy (SRPES) and low energy electron diffraction (LEED) are used to study the interaction between Ag atoms and the Si(1 1 1)1 × 1–H surface. At an Ag coverage of 0.063 monolayers (ML) on the Si(1 1 1)1 × 1–H surface, the Si 2p component corresponding to Si–H bonds decreases, and an additional Si 2p component appears which shifts to a lower binding energy by 109 meV with respect to the Si bulk peak. The new Si 2p component is also observed for 0.25 ML Ag on the Si(1 1 1)7 × 7 surface. These findings suggest that Ag atoms replace the H atoms of the Si(1 1 1)1 × 1–H surface and form direct Ag–Si bonds. Contrary to the widely accepted view that there is no chemical interaction between Ag particles and the H-passivated Si surface, these results are in good agreement with recent first-principles calculations.     

The adsorption of a substituted benzene,the ethynyl-trifluoro-toluene on Si(100)-2 × 1

The adsorption of 3-ethynyl-trifluoro-toluene (ETFT) on Si(100)-2 × 1 surface in ultra high vacuum is studied in the low coverage regime, through a joint experimental and theoretical approach. The STM images of both filled and empty states revealed few distinct adsorption configurations. On the basis of Density Functional Theory (DFT) calculations the STM images were simulated and three main adsorption configurations were identified, with a predominance of di-sigma bonded species that leave the benzene ring unreacted. A discussion of the reactivity of the reconstructed silicon surface towards benzene derivatives is proposed by comparing the adsorption of ETFT close related molecules, like styrene and phenylacetylene.     

Relative reactivities of amino and ethenyl groups in allylamine on Si(100)2 × 1: Temperature-dependent X-ray photoemission and thermal desorption studies of a common linker molecule

The room-temperature adsorption and thermal evolution of allylamine on Si(100)2 × 1 have been investigated by using temperature-dependent X-ray photoelectron spectroscopy (XPS) and thermal desorption spectrometry (TDS). The presence of a broad N 1 s feature at 398.9 eV, attributed to a N―Si bond, indicates N―H dissociative adsorption. On the other hand, the presence of C 1 s features at 284.6 eV and 286.2 eV, corresponding to C═C and C―N, respectively, and the absence of the Si―C feature expected at 283.2 eV shows that [2 + 2] C═C cycloaddition does not occur at room temperature. These XPS data are consistent with the unidentate staggered and eclipsed allylamine conformer adstructures arising from N―H dissociation and not [2 + 2] C═C cycloaddition. The apparent conversion of the N 1 s feature for Si―N(H)―C

at 398.9 eV to that for Si―N(H) at 397.7 eV and the total depletion of C 1 s feature for C―N at 286.2 eV near 740 K indicates cleavage of the C―N bond, leaving behind a Si―N(H) radical. Furthermore, the C═C C 1 s feature at 284.6 eV undergoes steep intensity reduction between 740 K and 825 K, above which a new C 1 s feature at 283.2 eV corresponding to SiC is found to emerge. These spectral changes suggest total dissociation of the ethenyl fragment and the formation of SiC. Moreover, while the total N 1 s intensity undergoes a minor reduction (24%) upon annealing up to 1090 K, a considerable reduction (43%) is found in the overall C 1 s intensity. This observation is consistent with our TDS data, which shows the desorption of C-containing molecules including propene and ethylene at 580 K and of acetylene at 700 K. The lack of N-containing desorbates suggests that the dissociated N species are likely bonded to multiple surface Si atoms or diffused into the bulk. Interestingly, both the staggered and eclipsed N―H dissociative adstructures are found to have a less negative adsorption energy than the [N, C, C] tridentate or the [2 + 2] C═C cycloaddition adstructures by our DFT calculations, which suggests that the observed formation of N―H dissociative adstructures is kinetically favored on the Si(100)2 × 1 surface.     

Second harmonic response of the Si(111)7 × 7 surface

Optical second harmonic generation spectra have been experimentally obtained from a clean Si(111) 7 × 7 in two different polarization configurations isolating the rotational anisotropic and isotropic contributions. The energy of the fundamental photon is varied from 0.8 eV to 2.5 eV. For comparison, we also use a microscopic formulation based on the semi-empirical tight binding method to evaluate the nonlinear surface susceptibility tensor χ(2ω). Good agreement between theory and experiment is obtained with respect to the number of resonances, their position in energy, and surface or bulk character.     

Self-assembly of C60 fullerenes on quasi-one-dimensional Si(111)4 × 1-In surface

Using scanning tunneling microscopy observations, self-assembly of C₆₀ fullerenes in the course of room-temperature adsorption onto Si(111)4 × 1-In reconstruction and after subsequent annealing at temperatures ranging from 150 to 450 °C has been studied. Adsorbed C₆₀ fullerenes have been found to occupy off-centered positions on In-atom rows forming linear chains with a maximal length of eight C₆₀ molecules. Intermolecular spacing within the regular chains equals three lattice constants of Si(111) surface. Two energetically different adsorption states of C₆₀ have been detected, one of which is occupied preferentially at room temperature, while occupation of the second (more tight) state dominates at temperature above ~ 150 °C. In the first state, C₆₀ fullerene resides plausibly in a continuous rotation, while in the second state a C₆₀ molecule is fixed tightly in a single orientation with a C₆₀ hexagon pointing upward. Transition of C₆₀ fullerenes to the more stable state is accompanied by expelling In atoms from the Si(111)4 × 1-In reconstruction.     

Atomic structure of Cs grown on Si(0 0 1)(2×1) surface by coaxial impact collision ion scattering spectroscopy

The atomic structure and the saturation coverage of Cs on the Si(0 0 1)(2×1) surface at room temperature have been studied by coaxial impact collision ion scattering spectroscopy (CAICISS). For the atomic structure of saturated Cs/Si(0 0 1)(2×1) surface, it is found that Cs atoms occupy a single adsorption site at T3 on the Si(0 0 1) surface. The height of Cs atoms adsorbed at T3 site is 3.18±0.05 Å from the second layer of Si(0 0 1)(2×1) surface. The saturation coverage estimated from the measured CAICISS intensity ratio and the proposed atomic structure is found to be 0.46±0.06 ML.     

Selective adsorption of coronene on Si(1 1 1)-(7 × 7)

The adsorption of coronene (C₂₄H₁₂) on the Si(1 1 1)-(7 × 7) surface is studied using scanning tunneling microscopy (STM). Upon room temperature submonolayer deposition, we find that the coronene molecules preferentially adsorb on the unfaulted half of the 7 × 7 unit cell. Molecules adsorbed on different sites can be induced to move to the preferential sites by the action of the tip in repeated image scans. Imaging of the molecules is strongly bias dependent, and also critically depends on the adsorption site. We analyze the results in terms of differential bonding strength for the different adsorption sites and we identify those substrate atoms which participate in the bonding with the molecule.