The adsorption of C6H5Cl on Si(111)7 × 7 studied by STM

The adsorption of chlorobenzene on Si(111)7 × 7 at room temperature was studied by scanning tunneling microscopy (STM). Selective chemisorption was observed at different adatom sites. It was found that the center adatoms were more reactive than the corner adatoms, and the faulted half of the unit cell was more reactive than the unfaulted. The mechanism is discussed in terms of the electronic and atomic structures in Si(111)7 × 7. Both preferences indicate that chlorobenzene was present initially in a mobile precursor state.     

Observation of triangular terraces and triangular craters of CaF2 film on Si(1 1 1) substrate

We have investigated the growth mode and surface morphology of CaF₂ film on Si(1 1 1)7×7 substrate by reflection high-energy electron diffraction (RHEED) using very weak electron beam and atomic force microscopy (AFM). It was found by RHEED intensity oscillation measurements and AFM observations that three-dimensional (3D) islands grow at RT; however, rather flat surface appears with two-dimensional (2D) islands around 300 °C. Especially, at high temperature of 700 °C, characteristic equilateral triangular terraces (or islands) with flat and wide shape grow with the tops directed toward [1 1 −2] of substrate Si(1 1 1). On the other hand, the desorption process of the CaF₂ film due to electron stimulated desorption (ESD) was also examined. It was found that the ESD process at 300 °C forms characteristic equilateral triangular craters on the film surface with the tops (or corners) directed toward [−1 −1 2] of substrate Si(1 1 1), provided that the film was grown at 700 °C.     

Rotational epitaxy of a hexagonal layered material on a square substrate: PbI2 on InSb(001)

PbI₂ has been adsorbed on the clean InSb(001)-(4 × 1) reconstructed surface and on the InSb(001)-(1 × 3)-Pb lead covered reconstructed surface. On the clean surface epitaxial growth occurred with the unit mesh of the layered PbI₂ aligning exactly with both the substrate [110] and [1 0] directions. On desorption a reaction occurred between the last layer of PbI₂, and the substrate, forming a series of structures which finished with a well-formed (1 × 3)-Pb structure in which the surface is depleted/enriched in In/Sb compared to the clean (4 × 1). The Pb in this structure is thought to partially replace surface In. Epitaxial adsorption also occurred on the (1 × 3)-Pb surface generating a single, well-formed structure with the hexagonal net of the PbI₂ aligned with just the [1 0] substrate direction. The structures and reactions are discussed and a row matching model is proposed to explain the single epitaxial orientation of PbI₂ on the (1 × 3)-Pb surface.     

Time evolution of interface roughness during thermal oxidation on Si(0 0 1)

The surface morphological change at an initial stage of thermal oxidation on Si(0 0 1) surface with O₂ was investigated as a function of oxide coverage by a real-time monitoring method of Auger electron spectroscopy (AES) combined with reflection high energy electron diffraction (RHEED). At 653 °C where oxide islands grow laterally, protrusions were observed to develop under the oxide islands as a consequence of concurrent etching of the surface. The rate of etching was measured from a periodic oscillation of RHEED half-order spot intensity I_(1/2,0) and I_(0,1/2). At 549 °C where Langmuir-type adsorption proceeds, it was observed that both I_(1/2,0) and I_(0,1/2) decrease more rapidly in comparison with an increase of oxide coverage and the intensity ratio between them decreases gradually with O₂ exposure time. These suggest that Langmuir-type adsorption occurs at sites where O₂ adsorbs randomly, leading to subdivision of the 2×1 and 1×2 domains by oxidized regions, and that Si atoms are ejected due to volume expansion in oxidation to change the ratio between 2×1 and 1×2 domains.     

Dissociative adsorption and site specificity in the initial stages of tetraethoxysilane (TEOS) interaction with Si(111)-(7×7)

We report results of a scanning tunneling microscopy and X-ray photoelectron spectroscopy study on the interaction of tetraethoxysilane (TEOS), a precursor for chemical vapor deposition of silicon dioxide, with Si(111)-(7×7) at room temperature. Under these conditions the interaction of TEOS with the surface is predominantly dissociative. The main adsorption products are ethyl- and triethoxysiloxane groups, which probably evolve in a four-center reaction of TEOS with two neighboring surface dangling bonds. Adsorption of the dissociation products is highly site-selective: triethoxysiloxane groups adsorb on the Si adatoms while ethyl groups react with the rest-atom dangling bonds. Center adatoms are over three times more reactive towards this reaction than corner adatoms. This two-fold selectivity is explained within the concept of local electron donor/acceptor properties.     

Surface structure evolution during Sb adsorption on Si(1 1 1)–In(4×1) reconstruction

The Sb adsorption process on the Si(1 1 1)–In(4×1) surface phase was studied in the temperature range 200–400 °C. The formation of a Si(1 1 1)–InSb (2×2) structure was observed between 0.5 and 0.7 ML of Sb. This reconstruction decomposes when the Sb coverage approaches 1 ML and Sb atoms rearrange to and (2×1) reconstructions; released In atoms agglomerate into islands of irregular shapes. During the phase transition process from InSb(2×2) to Sb (θ_Sb>0.7 ML), we observed the formation of a metastable (4×2) structure. Possible atomic arrangements of the InSb(2×2) and metastable (4×2) phases were discussed.     

The role of repulsive interactions in molecular bromine adsorption and patterning of Si(100)-2×1

Scanning tunneling microscopy (STM) was used to investigate the role of repulsive interactions in the adsorption and patterning of molecular bromine on the Si(100) surface. At room temperature and low coverage, chemisorption of bromine occurs dissociatively on the same side of adjacent dimers of the same row. Using the STM tip as a probe, we demonstrate the existence of repulsive interactions at adjacent sites on the Si(100)-2×1 surface. These repulsive interactions also contribute to the arrangement of adatoms on the surface. In particular, we report the presence of a stable c(4×2) surface phase that results after exposing the Si(100) surface to bromine under certain conditions. This phase involves adsorption on non-neighboring dimers and is stabilized by repulsive interactions that force bromine adatoms to occupy alternating dimers within rows with an out-of-phase occupancy between adjacent rows.     

Adsorption of oxygen and carbon dioxide on cesium-reconstructed Ag(1 1 0) surface

The adsorption of oxygen and carbon dioxide on cesium-reconstructed Ag(1 1 0) surface has been studied with scanning tunneling microscopy (STM) and temperature programmed desorption (TPD). At 0.1 ML Cs coverage the whole surface exhibits a mixture of (1 × 2) and (1 × 3) reconstructed structures, indicating that Cs atoms exert a cooperative effect on the surface structures. Real-time STM observation shows that silver atoms on the Cs-covered surface are highly mobile on the nanometer scale at 300 K. The Cs-reconstructed Ag(1 1 0) surface alters the structure formed by dissociative adsorption of oxygen from p(2 × 1) or c(6 × 2) to a p(3 × 5) structure which incorporates 1/3 ML Ag atoms, resulting in the formation of nanometer-sized (10–20 nm) islands. The Cs-induced reconstruction facilitates the adsorption of CO₂, which does not adsorb on unreconstructed, clean Ag(1 1 0). CO₂ adsorption leads to the formation of locally ordered (2 × 1) structures and linear (2 × 2) structures distributed inhomogeneously on the surface. Adsorbed CO₂ desorbs from the Cs-covered surface without accompanied O₂ desorption, ruling out carbonate as an intermediate. As a possible alternative, an oxalate-type surface complex [OOC–COO] is suggested, supported by the occurrence of extensive isotope exchange between oxygen atoms among CO₂(a). Direct interaction between CO₂ and Cs may become significant at higher Cs coverage (>0.3 ML).     

Chemisorption of isolated Br atoms on Si(100)-(2 × 1) studied by PAC

Chemisorption and desorption of isolated bromine adatoms on the Si(100)-(2 × 1) surface were investigated with nuclear methods. Br adsorption sites at low coverages of 10⁻³ monolayers (ML) were characterised by measuring the nuclear quadrupole interaction with perturbed γγ-angular correlation (PAC) of ⁷⁷Br→⁷⁷Se probe atoms. Below room temperature, two distinct adsorption sites for Br are revealed by PAC. One of them disappears after isochronal annealing above 300 K. The more stable probe-atom state is associated with single Br atoms saturating a dangling bond of the surface, while the less stable state is attributed to adsorption of Br at a bridge site. The potential barrier between the two adsorption sites is estimated to be 0.9(1) eV. At temperatures above 550 K, the fraction of atoms on distinct sites decreases, presumably due to surface diffusion. By measuring the γ-activity of the sample, complete desorption of the ⁷⁷Br atoms was observed above 620 K.     

Growth mode and interface structure of Ag on the HF-treated Si(111):H surface

A growth mode and interface structure analysis has been performed for Ag deposited at a high temperature of 300°C on the HF-treated Si(111):H surface by means of medium-energy ion scattering and elastic recoil detection analysis of hydrogen. The measurements show that Ag grows in the Volmer-Weber mode and that the Ag islands on the surface are epitaxial with respect to the substrate. The preferential azimuthal orientation is A-type only when Ag is deposited slowly. The interface does not reconstruct to the √3 × √3-Ag structure, which is normally observed for Ag deposition above 200°C on the Si(111)7 × 7 surface, but retain bulk-like structure. The presence of hydrogen at the interface is demonstrated after deposition of thick (1100 Å) Ag films. However, the amount of hydrogen at the interface is not a full monolayer. This partial desorption of hydrogen from the interface explains why the Schottky barrier heights of Ag/Si(111):H diodes are close to those of Ag/Si(111)7 × 7 and Ag/Si(111)2 × 1.     

Catalytic dehydrogenation and thermal chemistry of cyclohexene and 1-methyl-1,4-cyclohexadiene on Si(111)7 × 7

Recently, we reported a thermal desorption study on the evolution of an intense mass 78 profile for the room-temperature exposure of cyclohexene to Si(111)7 × 7 surface, which was believed to give rise to the formation of benzene by a surface dehydrogenation reaction. Because mass 78 was also found to be the base ion in the gas-phase cracking patterns of both 1,3- and 1,4-cyclohexadiene, the dehydrogenation of cyclohexene on clean, sputtered and oxidized Si(111)7 × 7 surfaces has been re-examined in order to determine the origin of the intense mass 78 desorption profile; i.e. whether it was in fact due to the evolution of benzene or cyclohexadiene, or both. Moreover, a similar dehydrogenation reaction giving rise to toluene desorption between 350 and 600 K has been observed for the room-temperature exposure of 1-methyl-1,4-cyclohexadiene to clean and sputtered Si(111)7 × 7 surfaces. The effects of methyl substitution on the reactivity of these cyclic olefins towards Si(111)7 × 7 can be inferred from these studies. Furthermore, the catalytic activity of Si(111)7 × 7 was found to be enhanced significantly by extending the thermal desorption cycles to a higher temperature of 925 K. The dehydrogenation of these olefins on Si(111)7 × 7 also gave rise to a unique 7 × 1 low energy electron diffraction pattern. Possible factors that may play a role in any proposed model for the dehydrogenation reaction are discussed. Finally, evidence of other surface reactions including cyclohexene hydrogénation to cyclohexane will also be presented.     

Surface electromigration of metals on Si(001): In/Si(001)

The possibility of surface electromigration (SE) of metals of In, Ga, Sb and Ag on a very flat Si(001)2×1 substrate (single domain 2×1) was examined by SEM, μ-RHEED and μ-AES under UHV conditions. It was found that Ga, Sb and Ag show no SE on Si(001) surface even at DC annealing temperatures for the desorption of these metals. For In on Si(001), a very fast SE (8000 μm/min) towards the cathode side was found that suddenly sets in at 450°C DC annealing, which was related to a surface phase transition. μ-RHEED and μ-AES observation showed that the SE is related to an ordered 4×3-In phase together with two-dimensional In gas phase over the 4×3-In phase and an In-disordered phase at the front end of SE. Single domain 4×3-In phases were found to occur under sequences of In deposition and DC annealing which involve the In SE on Si(001).     

Symmetry changes in He scattering from a Si(111) surface exposed to H atoms

Changes which occur on, and just below, the surface of a Si(111)-(7×7) crystal when it is dosed with H atoms are complex and still not well described. Measurements of He atom diffraction (HAS) from this surface in the [ 2 ] or [ 11] directions give scans which are asymmetric about the specular angle. The scans become symmetric when the surface is exposed to doses of H atoms sufficient to give coverages of 0.1 to 14 ML, if the atoms all stick. This means that the 3-fold rotational symmetry of the clean surface becomes 6-fold after the addition of the H atoms and shows that the faulted and unfaulted regions of the DAS model become equivalent as they are averaged by the He beam, although the large 49-atom unit cell remains. Thus this surface is not Si(111)-H(1×1), the equilibrated product of H-atom addition which is about 0.3 eV lower in energy, but a metastable intermediate state(s).

Comparison of results from HAS with those from other techniques, such as scanning tunneling microscopy, help to characterize this surface.     

Photon-stimulated desorption of methanol on Si(111)7 × 7 and Si(100)2 × 1 at the C 1s and O 1s thresholds

Photostimulated desorption experiments have been performed on deuterated methanol adsorbed on Si(111)7 × 7 and Si(100)2 × 1 at the C 1s and O 1s thresholds. D⁺ and the masses of the series CD⁺_x are produced in the photofragmentation process in both energy ranges. A comparison has been made with the photofragmentation spectra of methanol in the gas phase and two different desorption mechanisms have been hypothesized for the desorption of D⁺ and higher masses from the silicon surfaces at the C 1s threshold.     

Surface diffusion of Si,Ge and C adatoms on Si （001） substrate studied the molecular dynamics simulation

Depositions of Si, Ge and C atoms onto a preliminary Si (001) substrate at different temperatures are investigated by using the molecular dynamics method. The mechanism of atomic self-assembling occurring locally on the flat terraces between steps is suggested. Diffusion and arrangement patterns of adatoms at different temperatures are observed. At 900 K, the deposited atoms are more likely to form dimers in the perpendicular [110] direction due to the more favourable movement along the perpendicular [110] direction. C adatoms are more likely to break or reconstruct the dimers on the substrate surface and have larger diffusion distances than Ge and Si adatoms. Exchange between C adatoms and substrate atoms are obvious and the epitaxial thickness is small. Total potential energies of adatoms and substrate atoms involved in the simulation cell are computed. When a newly arrived adatom reaches the stable position, the potential energy of the system will decrease and the curves turns into a ladder-like shape. It is found that C adatoms can lead to more reduction of the system energy and the potential energy of the system will increase as temperature increases.     

Impact of the growth on the stability–instability transition at Si (111) during step bunching induced by electromigration

The central result of this work is the definite proof that the mechanisms of the direct current induced step bunching in the middle and high temperature domains are different. We used the recently developed technique for reflection electron microscopy (REM) observation of Si surfaces during equilibrium and during crystal growth to document the impact of the growth on the process of step bunching induced by direct current heating of an Si crystal. We found completely different effects of crystal growth on the stability of the vicinal surfaces in the two temperature domains 1160–1240°C and 1260–1320°C. In the high temperature domain step bunching takes place at step-down direction of the electric current during sublimation, equilibrium and growth; whereas in the 1160–1240°C domain bunching takes place at step-up current during sublimation and at step-down current during growth. These findings support the concept of local mass transport in the high temperature domain — the surface migration of adatoms is effectively interrupted at each step by a high rate exchange between the adlayer and the crystal phase. At 1160–1240°C the mass transport is global — adatoms easily cross the steps without taking part in the crystal–adlayer exchange. Since earlier studies of other researchers support the concept of local mass transport in the low temperature domain, 900–1050°C, a difficult question arises — why do the properties of the steps, with respect to the mass transport over the crystal surface, have a temperature dependence which is not monotonous? To explain the transition from local mass transport in the low temperature domain to global mass transport in the middle temperature domain we advance a hypothesis for a transition from a low temperature state of adsorption (Takayanagi-like adatoms, existing above the (7×7)↔(1×1) transition) to a high temperature state of adsorption (adatom with three dangling bonds) with much lower activation energy for desorption.     

Ga-induced superstructures on the Si(1 1 1) 7 × 7 surface

Monolayer Ga adsorption on Si surfaces has been studied with the aim of forming p-delta doped nanostructures. Ga surface phases on Si can be nitrided by N₂⁺ ion bombardment to form GaN nanostructures with exotic electron confinement properties for novel optoelectronic devices. In this study, we report the adsorption of Ga in the submonolayer regime on 7 × 7 reconstructed Si(1 1 1) surface at room temperature, under controlled ultrahigh vacuum conditions. We use in-situ Auger electron spectroscopy, electron energy loss spectroscopy and low energy electron diffraction to monitor the growth and determine the properties. We observe that Ga grows in the Stranski-Krastanov growth mode, where islands begin to form on two flat monolayers. The variation in the dangling bond density is observed during the interface evolution by monitoring the Si (LVV) line shape. The Ga adsorbed system is subjected to thermal annealing and the residual thermal desorption studied. The difference in the adsorption kinetics and desorption dynamics on the surface morphology is explained in terms of strain relaxation routes and bonding configurations. Due to the presence of an energetic hierarchy of residence sites of adatoms, site we also plot a 2D phase diagram consisting of several surface phases. Our EELS results show that the electronic properties of the surface phases are unique to their respective structural arrangement.     

The structure of Na adsorbed on Ge(1 0 0) and its influence on substrate morphology

We investigated the adsorption of sodium on the (1 0 0) surface of germanium with LEED, STM and electron spectroscopy (XPS). Upon adsorption at room temperature a metastable p(4 × 1) and a p(2 × 1) superstructure have been found. Annealing of these structures, accompanied by thermal desorption, results in the formation of a commensurate p(3 × 2) phase after an incommensurate state has been passed. The formation of structures observed after annealing requires the rearrangement of substrate atoms. In addition strong evidence was found that all ordered phases discussed in this paper contain one adsorbate atom per unit mesh.     

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.     

Investigation of hydrogen interaction with the Si(1 1 1)-7 × 7 surface by STM with Bi/W tips

The STM technique with a special Bi/W tip was used to study the interaction of hydrogen atoms with the Si(1 1 1)-7 × 7 surface. The reactivity of different room temperature (RT) adsorption sites, such as adatoms (A), rest atoms (R), and corner holes (CH) was investigated. The reactivity of CH sites was found to be ∼2 times less than that of R and A sites. At temperatures higher than RT, hydrogen atoms rearrange among A, R, and CH sites, with increased occupation of R sites (T <  300 °C). Further temperature increase leads to hydrogen desorption, where its surface diffusion plays an active role. We discuss one of the possible desorption mechanisms, with the corner holes surrounded by a high potential barrier. Hydrogen atoms have a higher probability to overcome the desorption barrier rather than diffuse either into or out of the corner hole. The desorption temperature of hydrogen from CH, R, and A sites is about the same, equal to ∼500 °C. Also it is shown that hydrogen adsorption on the CH site causes slight electric charge redistribution over neighbouring adatoms, namely, increases the occupation of electronic states on A sites in the unfaulted halves of the Si(1 1 1)-7 × 7 unit cell. Based on these findings, the indirect method of investigation with conventional W tips was suggested for adsorbate interaction with CH sites.