Structural study of Si(1 1 1)-6 × 1-Ag surface using surface X-ray diffraction

The surface structure of Si(1 1 1)-6 × 1-Ag was investigated using surface X-ray diffraction techniques. By analyzing the CTR scattering intensities along 00 rod, the positions of the Ag and reconstructed Si atoms perpendicular to the surface were determined. The results agreed well with the HCC model proposed for a 3 × 1 structure induced by alkali-metals on a Si(1 1 1) substrate. The heights of the surface Ag and Si atoms did not move when the surface structure changed from Si(1 1 1)-√3 × √3-Ag to Si(1 1 1)-6 × 1-Ag by the desorption of the Ag atoms. From the GIXD measurement, the in-plane arrangement of the surface Ag atoms was determined. The results indicate that the Ag atoms move large distances at the phase transition between the 6 × 1 and 3 × 1 structures.     

Structural analysis of Si(1 1 1)-√21 × √21-Ag surface by reflection high-energy positron diffraction

The atomic structure of Si(1 1 1)-√21 × √21-Ag surface, which is formed by the adsorption of small amount of Ag atoms on the Si(1 1 1)-√3 × √3-Ag surface, was determined by using reflection high-energy positron diffraction. The rocking curve measured from the Si(1 1 1)-√21 × √21-Ag surface was analyzed by means of the intensity calculations based on the dynamical diffraction theory. The adatom height of the extra Ag atoms from the underlying Ag layer was determined to be 0.53 Å with a coverage of 0.14 ML, which corresponds to three atoms in the √21 × √21 unit cell. From the pattern analyses, the most appropriate adsorption sites of the extra Ag atoms were proposed.     

Fabrication and scanning tunneling microscopy studies of the Si(1 1 1)-(√31 × √31)-In surface

We report on the fabrication of single phase of the Si(1 1 1)-(√31 × √31)-In reconstruction surface, observed by scanning tunneling microscopy (STM) at room temperature. By depositing specific amounts of indium atoms while heating the Si(1 1 1)-(7 × 7) substrate at a critical temperature, the single phase of Si(1 1 1)-(√31 × √31)-In surfaces could be routinely obtained over the whole surface with large domains. This procedure is certified by our high-resolution STM images in the range of 5-700 nm. Besides, the high resolution STM images of the Si(1 1 1)-(√31 × √31)-In surface were also presented.     

Structural analysis of Si(1 1 1)-√21 × √21-(Ag, Au) surface by using reflection high-energy positron diffraction

The Au adsorption induced √21 × √21 super-lattice structure on the Si(1 1 1)-√3 × √3-Ag structure has been investigated using reflection high-energy positron diffraction. The height of the Au adatom was determined to be 0.59 Å from the underlying Ag layer from the rocking curve analysis with the dynamical diffraction theory. The adatoms were preferentially situated at the center of the large Ag triangle of the inequivalent triangle structure of the Si(1 1 1)-√3 × √3-Ag substrate. From the intensity distribution in the fractional-order Laue zone, the in-plane coordinate of the Au adatoms was obtained.     

Unoccupied band dispersion of Si(1 1 1):√3 × √3-Ag surface studied by time- and angle-resolved two-photon photoemission spectroscopy

Band dispersion and transient population of unoccupied electronic states on Si(1 1 1):√3 × √3-Ag surface have been studied by time-resolved (TR) and angle-resolved (AR) two-photon photoemission (2PPE) spectroscopy. The band dispersions originating from unoccupied electronic states have been identified from the comparison between AR-2PPE spectra and angle-resolved one-photon photoemission spectra with synchrotron radiation. A lifetime of unoccupied surface state has been determined from the TR-2PPE spectra.     

Fabrication of uniform Au silicide islands on the Si(1 1 1)-(7 × 7) substrate

The Au silicide islands have been fabricated by additional deposition of Au on the prepared surface at 270 °C where the Si islands of magic sizes were formed on the Si(1 1 1)-(7 × 7) dimer-adatom-stacking fault substrate. The surface structure on the Au silicide islands shows the Au/Si(1 1 1)-√3 × √3 reconstructed structure although the substrate remains 7 × 7 DAS structure. The size of the Au silicide islands depends on the size distribution of the preformed Si islands, because the initial size and shape of the Si islands play important roles in the formation of the Au silicide island. We have achieved the fabrication of the Au silicide islands of about the same size (∼5 nm) and the same shape by controlling the initial Si growth and the additional Au growth conditions.     

Atomic structure of Cs layer grown on Si(0 0 1)(2 × 1) surface at room temperature

The atomic structure of Cs atoms adsorbed on the Si(0 0 1)(2 × 1) surface has been investigated by coaxial impact collision ion scattering spectroscopy. When 0.5 ML of Cs atoms are adsorbed on Si(0 0 1) at room temperature, it is found that Cs atoms occupy a single absorption site on T3 with a height of 3.18 ± 0.05 Å from the second layer of Si(0 0 1)(2 × 1) surface, and the bond length between Cs and the nearest Si atoms is 3.71 ± 0.05 Å.     

Surface structure and phase transition of Ge(1 1 1)-3 × 3-Pb studied by reflection high-energy positron diffraction

We studied the structures and the phase transition of Pb/Ge(1 1 1) surface by using the reflection high-energy positron diffraction. The surface structures at 60 K and 293 K have the 3 × 3 and √3 × √3 periodicities, respectively. The rocking curves measured at both temperatures are nearly the same. This indicates that the equilibrium positions of the surface atoms do not change according to the phase transition. From the analysis of the rocking curve based on the dynamical diffraction theory, we found that at both temperatures the surface structures are composed of the so-called one-up and two-down model. The 3 × 3-√3 × √3 phase transition for the Pb/Ge(1 1 1) surface is interpreted in terms of order-disorder transition.     

Reconstructions 3 × 3 and √3 × √3 on SiC(0 0 0 1) studied using RHEED

The 3 × 3 and √3 × √3 reconstructions on 6H-SiC(0 0 0 1) surface were obtained via depositing thin silicon layer and annealing it in ultrahigh vacuum (without Si flux). Rocking curves of reflection high energy electron diffraction (RHEED) were measured for integer and fractional order beams. They were fitted with results of many-beam calculation on the basis of dynamical theory of RHEED to determine structural parameters. For √3 × √3 superstructure, it was found that the occupancy of adatom states is 0.45 (incomplete coverage). In the sequence of Si-C double layers ABCACB, the lattice is terminated with the layer A. For 3 × 3 superstructure, the rocking curves support the model with twisted tetra-cluster. The best-fit twist is as half of that predicted in ab initio calculations; it is due to limited source of Si atoms to build up the superstructure. Larger twist correlates with higher occupancy of corner sites and with slower cooling rate of the sample after annealing.     

Study of buried Si(1 1 1)-5 × 2-Au by surface X-ray diffraction

The structure of buried Si(1 1 1)-5 × 2-Au capped with amorphous Si was investigated using surface X-ray diffraction. It was found that the 5 × 2 structural periodicity is kept under the amorphous Si from the in-plane measurement. Furthermore, the intensity variation along the fractional-order rod indicates that Au atoms are located almost on the same plane.     

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.     

Surface electronic structure of the (3 × 2) reconstruction induced by Yb on a Si(1 1 1) surface

We have investigated the electronic structure of the Yb/Si(1 1 1)-(3 × 2) surface using angle-resolved photoelectron spectroscopy. Five surface states have been identified in the gap of the bulk band projection. Among these five surface state, the dispersions of three of them agree well with those of the surface states of monovalent atom adsorbed Si(1 1 1)-(3 × 1) surfaces. The dispersions of the two other surface states agree well with those observed on the Ca/Si(1 1 1)-(3 × 2) surface, whose basic structure is the same as that of monovalent atom adsorbed Si(1 1 1)-(3 × 1) surfaces. Taking these results into account, we conclude that the five surface states observed in the band gap originate from the orbitals of Si atoms that form a honeycomb-chain-channel structure.     

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.     

Fabrication of nanostructures by selective growth of C60 and Si on Si(1 1 1) substrate

Using two types of selective growth, selective C₆₀ growth and selective Si growth, on a common Si(1 1 1) substrate, an array of C₆₀ nanoribbons with controlled values of width and thickness is fabricated. On a surface that has Si(1 1 1)√3 × √3R30°-Ag (referred to as Si(1 1 1)√3-Ag hereafter) and bare Si(1 1 1) regions at the same time, the preferential growth of C₆₀ multilayered film is recognized on the Si(1 1 1)√3-Ag region. The growth of Si selectively occurs on a bare Si(1 1 1) region if the substrate surface has C₆₀-adsorbed and bare Si(1 1 1) regions at the same time. As a demonstration of the use of these selective growths, we fabricate an array of well-isolated C₆₀ nanoribbons, which show a well-ordered molecular arrangement and have sizes of about 40 nm in widths and 3-4 nm in thicknesses.     

A structural parallel between Ge- and Si-induced 4 × 4 and 3 × 3 reconstructions on SiC(0 0 0 1) drawn from comparative RHEED oscillations

The initial Ge growth stages on a (√3 × √3)R30°-reconstructed SiC(0 0 0 1) surface (√3) have been studied using a complete set of surface techniques such as reflection high energy electron diffraction (RHEED), low energy electron diffraction (LEED), atomic force microscopy (AFM) and photoemission and compared with similar Si surface enrichments in place of Ge. The investigations essentially focus on the wetting growth-regimes that are favoured by the use of the √3 surface as a starting substrate, this surface being the closest to a smooth and ideally truncated Si-terminated face of hexagonal SiC(0 0 0 1). Depending on temperature and Ge or Si coverages, varying surface organizations are obtained. They range from unorganized layer by layer growths to relaxed Ge(1 1 1) or Si(1 1 1) island growths, through intermediate attempts of coherent and strained Ge or Si surface layers, characterized by 4 × 4 and 3 × 3 surface reconstructions, respectively. RHEED intensity oscillation recordings, as a function of Ge or Si deposited amounts, have been particularly helpful to pinpoint the limited (by the high lattice mismatch) existence domains of these interesting coherent phases, either in terms of formation temperature or surface coverages. Prominently comparable data for these two Ge- and Si-related reconstructions allow us to propose an atomic model for the still unexplained Ge-4 × 4 one. It is based on a same local organization in trimer and ad-atom units for the Ge excess as admitted for the Si-excess of the 3 × 3 surface, the higher strain nevertheless favouring arrangements, for the Ge-units, in 4 × 4 arrays instead of 3 × 3 Si ones. Admitting such models, 1.25 and 1.44 monolayers of Ge and Si, should, respectively, be able to lie coherently on SiC, with respective lattice mismatches near 30% and 25%. The experimental RHEED-oscillations values are compatible with such theoretical ones. Moreover, these RHEED coverage determinations (for layer completion, for instance) inform us in turn about the initial Si richness of the starting √3 reconstruction and help us to discriminate between earlier contradictory atomic models proposed in the literature.     

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.     

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.     

Spectroscopic interpretation for Na-induced phase transitions on Na/Si(1 1 1)3 × 1

Na adsorption at room temperature causes the Na/Si(1 1 1)3 × 1 surface with Na coverage of 1/3 monolayer (ML) to transit into the Na/Si(1 1 1)6 × 1 surface at 1/2 ML and sequentially into the Na/Si(1 1 1)3 × 1 surface at 2/3 ML. The phase transition was studied by Si 2p core-level photoemission spectroscopy. The detailed line shape analysis of the Si 2p core-level spectrum of the Na/Si(1 1 1)3 × 1 surface (2/3 ML) is presented and compared to the Na/Si(1 1 1)3 × 1 surface (1/3 ML) which is composed of Si honeycomb chain-channel structures. This suggests that as additional Na atoms form atomic chains resulting in the Na/Si(1 1 1)3 × 1 surface (2/3 ML), the inner atoms of the Si honeycomb chain-channel structure is buckled due to the additional Na atoms.     

Investigation of the (√3 × √3)R30°-Cu2Si/Cu(1 1 1) surface alloy using DFT

The electronic structure of the FCC, HCP and 2-fold bridge phases of the (√3 × √3)R30°-Cu₂Si/Cu(1 1 1) surface alloy have been investigated using LCAO-DFT. Analysis of the total electron density, partial density-of-states (PDOS) and crystal orbital overlap population (COOP) curves for the system have shown a surprising similarity between the intra- and inter-layer Si-Cu bond for each phase. Low hybridization between the Si 3s and 3p orbitals results in a low directionality of the Si-Cu bond within each of phase. The Si 3s orbitals are shown to form covalent bonds with their surrounding Cu atoms whereas the Si 3p and 3d orbitals are shown to form combinations of covalent and metallic bonds. The Si-Cu interaction is shown clearly to extend to the second layer of the alloy in deference to previous studies of Si/Cu alloys.     

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.