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.     

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.     

Edge-dimer row - The reason of three-bilayer steps and islands stability on Si(1 1 1)-7 × 7

A hypothesis of perpendicular dimer row formation along three-bilayer (3 BL) step was suggested. The hypothesis, explains the stability of 3 BL steps on the vicinal Si(1 1 1) surface deflected in direction as well as the limitation of Ge and Si island height by 3 BL at the initial nucleation stages on Si(1 1 1) surface. The detailed examinations of STM images of 3 BL steps were carried out. New peculiarities of atomic structure of 3 BL single step on Si(1 1 1) and 3 BL steps on Si(5 5 7) surfaces were revealed. The results of STM images examination verify the hypothesis of perpendicular dimer row formation along the boundary of the 3 BL step.     

Reversible electromigration of thallium adatoms on the Si(1 1 1) surface

By means of low-energy electron diffraction (LEED), we found a reversible structural change of on thallium (Tl) adsorbed Si(1 1 1) surfaces by switching the polarity of applied DC voltage for heating the sample. It was shown in the literature that Tl adatoms are located on the T₄ sites of the bulk-terminated surface both in the (1 × 1) and . It is clarified that the structural change is caused by the electromigration of the Tl adatoms. Tl atoms migrate towards the cathode, being induced by the electric field (10-20 V/cm). We discussed an atomic process of the electromigration.     

Electronic structure of the Sb-induced Si(1 1 3)2 × 5 surface

The surface electronic structure of Sb/Si(1 1 3)2 × 5 was investigated by angle-resolved photoemission spectroscopy experiments. This reveals Sb/Si(1 1 3)2 × 5 to have three surface bands with anisotropic two-dimensional characteristics. The band widths of the surface bands along is larger than along . The number of surface bands of Sb/Si(1 1 3)2 × 5 and their band dispersions along and are quite analogous with those of Sb/Si(1 1 3)2 × 2 composed of Sb adatom and Si tetramer chains. The electronic structure analogy suggests that Sb/Si(1 1 3)2 × 5 and Sb/Si(1 1 3)2 × 2 have common building blocks such as Sb adatom and Si tetramer chains.     

An ab initio-based approach to adsorption-desorption behavior of Si adatoms on GaAs(1 1 1)A-(2 × 2) surfaces

The adsorption-desorption behavior of Si adatoms on GaAs(1 1 1)A-(2 × 2) surfaces is investigated using our ab initio-based approach, in which adsorption and desorption behavior of Si adatoms is described by comparing the calculated desorption energy obtained by total-energy electronic-structure calculations with the chemical potential estimated by quantum statistical mechanics. We find that the Si adsorption at the Ga-vacancy site on the (2 × 2) surfaces with As adatoms occurs less than 1140-1590 K while the adsorption without As adatom does less than 630-900 K. The change in adsorption temperature of Si adatoms by As adatoms is due to self-surfactant effects of As adatoms: the promotion of the Si adsorption triggered by As adatoms is found to be interpreted in terms of the band-energy stabilization. Furthermore, the stable temperature range for Si adsorbed surfaces with As adatoms agrees with the experimental results. The obtained results provide a firm theoretical framework to clarify n-type doping processes during GaAs epitaxial growth.     

Structural and statistical analysis of Yb/Si(1 1 1) and Eu/Si(1 1 1) reconstructions

We have performed the structural and statistical analysis of Yb/Si(1 1 1) and Eu/Si(1 1 1) surfaces in the submonolayer regime utilizing low-energy electron diffraction and scanning tunneling microscopy (STM). The almost identical series of one-dimensional chain structures (e.g., 3 × 2/3 × 1, 5 × 1, 7 × 1, 9 × 1, and 2 × 1 phases) are found in order of increasing metal coverage for both adsorbed systems, however, only the Eu/Si system reveals the ‘√3’-like reconstruction before the 2 × 1 endpoint phase. The atomic models of chain structures are proposed and discussed. In particular, our results suggest the odd-order n×1 (n=5,7,9,…) intermediate reconstructions to incorporate the Seiwatz chains and honeycomb chains with the proportion of m:1, where . The statistical analysis of STM images is carried out to examine the correlation of atomic rows on Eu/Si and Yb/Si surfaces. It is found that Eu stabilizes more ordered row configuration compared to Yb, which can be explained in terms of indirect electronic interaction of atomic chains or/and different magnetic properties of adsorbed species.     

Isomeric effects on room-temperature chemisorption and thermal evolution of iso-, cis- and trans-dichloroethylene on Si(1 1 1)7 × 7

The room-temperature adsorption and thermal evolution of iso-, cis- and trans-dichloroethylene (DCE) on Si(1 1 1)7 × 7 have been studied by vibrational electron energy loss spectroscopy and thermal desorption spectrometry (TDS). The presence of the Si-Cl stretch at 510 cm⁻¹ suggests that, upon adsorption, all three isomers dissociate via C-Cl bond breakage on the 7 × 7 surface to form mono-σ bonded chlorovinyl , which could, in the case of iso-DCE, further dechlorinate to vinylidene (:CCH₂) upon insertion into the back-bond. The higher saturation exposure for the Si-Cl stretch at 510 cm⁻¹ observed for cis- and trans-DCE than iso-DCE suggests that Cl dissociation via the CHCl group in the cis and trans isomers is less readily than the CCl₂ group in iso-DCE. Our TDS data show remarkable similarities in both molecular desorption near 360 K and thermal evolution of the respective adstructures for all three isomers on Si(1 1 1)7 × 7. In particular, upon annealing to 450 K, the mono-σ bonded chlorovinyl adspecies is found to further dechlorinate to either vinylene di-σ bonded to the Si surface or acetylene to be released from the surface. Above 580 K, vinylene could also become gaseous acetylene or undergo H abstraction to produce hydrocarbon or SiC fragments. All three DCE isomers also exhibit TDS features attributable to an etching product SiCl₂ at 800-950 K and recombinative desorption products HCl at 700-900 K and H₂ at 650-820 K. The stronger Cl-derived TDS signals and Si-Cl stretch at 510 cm⁻¹ over 450-820 K for trans-DCE than those for cis-DCE indicate stronger dechlorination for trans-DCE than cis-DCE, which could be due to less steric hindrance resulting from the formation of the chlorovinyl adspecies for trans-DCE during the initial adsorption/dechlorination process. Finally, our density functional calculations qualitatively support the thermodynamic feasibility and relative stabilities of the proposed adstructures involving chlorovinyl, vinylidene, and vinylene adspecies.     

Scanning tunneling microscopy study on initial stage of atomic hydrogen adsorption on the Si(1 1 1) 7 × 7 surface

Initial hydrogen adsorption on the Si(1 1 1) 7 × 7 surface was studied by scanning tunneling microscopy (STM) in an ultrahigh vacuum. Room temperature adsorbed hydrogen on the adatom in the 7 × 7 reconstruction led to depression of adatoms in the STM images. The hydrogen uptake curve at the adatom site as a function of hydrogen exposure time was well represented by Langmuir adsorption. No preferential adsorption was seen among four inequivalent adatoms in the 7 × 7 reconstruction. Adsorption of the adjacent center and corner adatoms respectively showed ∼10% higher adsorption. Even though the number of reacted adatoms in the half unit of the 7 × 7 reconstruction was statistically random, the number of reacted adatoms in the nearest neighbor half unit was enhanced as the number of reacted sites increased in the half unit.     

Aromatic interactions in the close packing of phenyl-imides at Cu(1 1 0) surfaces

The oxidation of aniline at Cu(1 1 0) surfaces at 290 K has been studied by XPS and STM. A single chemisorbed product, assigned to a phenyl imide (C₆H₅N(a)), is formed together with water which desorbs. Reaction with preadsorbed oxygen results in a maximum surface concentration of phenyl imide of 2.8 × 10¹⁴ mol cm⁻² and a surface dominated by domains of three structures described by , and unit meshes. However, concentrations of phenyl imide of up to 3.3 × 10¹⁴ mol cm⁻² were obtained from the coadsorption of aniline and dioxygen (300:1 mixture) resulting in a highly ordered biphasic structure with and domains. Comparison of the STM and XPS data shows that only half the phenyl imides at the surface are imaged. Pi-stacking of the phenyl rings is proposed to account for this observation.     

X-ray initiated molecular photochemistry of Cl-containing adsorbates on a Si(1 0 0) surface using synchrotron radiation

X-ray initiated molecular photochemistry for SiCl₄ and CCl₄ adsorbed on Si(1 0 0) at ∼90 K following Cl 2p core-level excitation is investigated by photon stimulated ion desorption and ion kinetic energy distribution measurements. The Cl excitation of solid SiCl₄ induces the significant enhancement (∼900%) of the Cl⁺ yield, while the Cl excitation of condensed CCl₄ leads to a moderate enhancement (∼500%) of the Cl⁺ yield. The enhancement of Cl⁺ yield at the specific core-excited states is strongly correlated to the ion escaped energy. Upon X-ray exposure for CCl₄ adsorbed on Si(1 0 0) (20-L exposure), the Cl⁺ yields at resonances decrease and new structures at higher photon energies are observed. Cl⁺ yields at these new resonances are significantly enhanced compared to those at other resonances. These changes are the results of desorption and surface reaction of the CCl₄-Si surface complex due to X-ray irradiation. We have demonstrated that state-specific enhancement of ion desorption can be successfully applied to characterize the reaction dynamics of adsorbates adsorbed on surfaces by X-ray irradiation.     

Ge adsorption on SiC(0 0 0 1): An ab initio study

In this work we have performed an ab initio total energy investigation of the Ge adsorption process on the Si-terminated SiC(0 0 0 1)- and (3 × 3) surfaces. We find that Ge adatoms lying on the topmost sites of the and (3 × 3) surfaces represent the energetically more stable configurations at the initial stage of the Ge adsorption on the SiC(0 0 0 1) surface. The Si → Ge substitutional adsorption processes have been examined as a function of the Si and Ge chemical potentials. Increasing the Ge coverage, we verify that the formation of Ge wetting layer on the surface, and Ge nanocluster on the (3 × 3) surface are the energetically more stable configurations, in accordance with recent experimental findings.     

Direct STM evidence for Cu-benzoate surface complexes on Cu(1 1 0)

The chemisorption of benzoate on a Cu(1 1 0) crystal at room temperature was studied using low temperature scanning tunneling microscopy. STM images, obtained at 5 K for low benzoate coverage, show isolated surface species that consist of a single Cu adatom stabilizing two benzoate molecules in a flat orientation. These species are discussed in relation to other known metal-organic surface compounds. At higher coverage the overlayer, called the α-phase, was also observed at 5 K and found to contain features attributable to two Cu adatoms associated with two pairs of non-equivalent benzoate species. The observed topographic features are used to suggest refinements of the structural model of the ordered α-phase overlayer.     

Adsorption structure of germanium on the Ru(0 0 0 1) surface

Coverage-dependent adsorption energy of the Ge/Ru(0 0 0 1) growth system and the geometrical distortions of the most stable adsorption structure are investigated through first-principles calculations within density functional theory. A local minimum in adsorption energy is found to be at a Ge coverage of 1/7 monolayer with a Ru(0 0 0 1)- symmetry. Based on this stale superstructure, the scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) images are simulated by means of surface local-density of states (LDOS). The results are consistent well with the STM measurements on the phase for Ge overlayer on Ru(0 0 0 1). From this stimulation, the relations between the STM images and the lattice distortion are also clarified.     

Co-induced nano-structures on Si(1 1 1) surface

The interaction of cobalt atoms with silicon (1 1 1) surface has been investigated by means of scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED). Besides the Co silicide islands, we have successfully distinguished two inequivalent Co-induced reconstructions on Si(1 1 1) surface. Our high-resolution STM images provide some structural properties of the two different derived phases. Both of the two phases seem to form islands with single domain. The new findings will help us to understand the early stage of Co silicide formations.     

Reactions of atomic oxygen with the D-covered Si(1 0 0) surfaces

We have studied D abstraction by O on the D/Si(1 0 0) surfaces using a continuous as well as pulsed O-beams. Both D₂ and D₂O molecules are detected during O-exposure. The D₂ desorption is found to take place more efficiently on the monodeuteride/dideuteride surface than on the monodeuteride surface. The pulsed beam experiments exhibit occurrence of both a slow and a fast D₂ desorption. The D₂ desorption is found to obey the second-order rate law in on the monodeuteride surfaces and 3.5th-order rate law on the monodeuteride/dideuteride surfaces. The D₂O desorption is found to be governed also by the second-order rate law, however regardless of D coverage even on the monodeuteride/dideuteride surfaces. Possible mechanisms for the O-induced desorption from the D/Si(1 0 0) surfaces are discussed.     

Atomic structure of thin dysprosium-silicide layers on Si(1 1 1)

We report on scanning tunneling microscopy results of thin dysprosium-silicide layers formed on Si(1 1 1). In the submonolayer regime, both a and a 5 × 2 superstructure were found. Based on images taken at different tunneling conditions, a structure model could be developed for the superstructure. For one monolayer, a 1 × 1 superstructure based on hexagonal DySi₂ was observed, while several monolayers thick films are characterized by a superstructure from Dy₃Si₅.     

Influence of the ultra-thin Ag layer on Si(1 1 1)7 × 7 on directional elastic peak electron spectroscopy profiles

The directional elastic peak electron spectroscopy (DEPES) polar profiles for the clean Si(1 1 1)7 × 7 surface and the Si(1 1 1)√ 3 × √3R30°-Ag system are presented. The results were obtained for the and azimuths of the substrate for primary electron energies from the range 0.5-2 keV. A simple qualitative analysis of the observed profiles revealed the influence of the ultra-thin silver layer on the shape of the measured DEPES polar profiles, i.e. both on their background level and on the height of some intensity maxima. Thus, the information on the position of silver atoms in the investigated structure and other ultra-thin layers on crystalline substrates seems to be obtainable by the analysis of the DEPES profiles. The presence of numerous maxima in the measured profiles imply the application of a more advanced method in qualitative and quantitative interpretation of the DEPES profiles.