Changes of phase and intensity of optical SHG with Ag deposition on Si(111)-7×7 surfaces

The phase and intensity of optical second harmonic generation (SHG) were studied in Ag deposition on the Si(1 1 1) surfaces. The 7×7 reconstruction of the surface changed to the 1×1 structure in room temperature deposition. The SHG intensity reduced and the phase shifted to +180° with this structural change. Meanwhile, the 7×7 reconstruction changed to the reconstruction in 400 °C deposition. With this structural change, the SHG intensity increased and the phase shifted to −250°. An analysis with anharmonic oscillator model showed that the changes in room temperature deposition were due to the quenching of the surface dangling bond states of the 7×7 reconstruction by the Ag deposition, whereas those in 400 °C deposition were due to the appearance of new surface states of the reconstruction.     

Surface reconstructions of the Si(100)–Ge system

The surface reconstruction of epitaxial Ge layer on Si(100) was studied with ultrahigh vacuum scanning tunneling microscopy. The surface with 0.8 ML Ge grown in the presence of a hydrogen surfactant reveals the same structures as found in chemical-vapor-deposited Ge on Si(100): (i) defective (2×1) structure at 290°C, (ii) irregular (2×N) in Ge layer and defective (2×1) in bare Si regions at 420°C, and (iii) (2×N) in Ge-covered regions and c(4×4) in bare Si regions at 570°C. The morphology of step edges does not change with temperature, implying that the c(4×4) reconstruction is anisotropic in nature.     

Well-ordered (1 0 0) InAs surfaces using wet chemical treatments

Atomic ordering of HCl-isopropanol (HCl-iPA) treated and vacuum annealed (1 0 0) InAs surfaces was studied by scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and reflectance anisotropy spectroscopy (RAS). On the as-treated surface, a diffused (1 × 1) pattern is observed, which successively evolves to the β₂(2 × 4)/c(2 × 8) and (4 × 2)/c(8 × 2) ones after annealing to 330 °C and 410 °C, respectively. At the intermediate temperature of 370 °C, an ₂(2 × 4)/(4 × 2) mixed reconstruction is observed. Reflectance anisotropy spectra are compared with those of the corresponding reconstructions observed after As-decapping and found to be quite similar. Therefore we conclude that high-quality (1 0 0) InAs surfaces can be obtained by wet chemical treatment in an easy, inexpensive and practical way.     

Structures of sulfur on TiO2(1 1 0) determined by scanning tunneling microscopy, X-ray photoelectron spectroscopy and low-energy electron diffraction

The temperature dependent adsorption of sulfur on TiO₂(1 1 0) has been studied with X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), and low-energy electron diffraction (LEED). Sulfur adsorbs dissociatively at room temperature and binds to fivefold coordinated Ti atoms. Upon heating to 120°C, 80% of the sulfur desorbs and the S 2p peak position changes from 164.3±0.1 to 162.5±0.1 eV. This peak shift corresponds to a change of the adsorption site to the position of the bridging oxygen atoms of TiO₂(1 1 0). Further heating causes little change in S coverage and XPS binding energies, up to a temperature of 430°C where most of the S desorbs and the S 2p peak shifts back to higher binding energy. Sulfur adsorption at 150°C, 200°C, and 300°C leads to a rich variety of structures and adsorption sites as observed with LEED and STM. At low coverages, sulfur occupies the position of the bridging oxygen atoms. At 200°C these S atoms arrange in a (3×1) superstructure. For adsorption between 300°C and 400°C a (3×3) and (4×1) LEED pattern is observed for intermediate and saturation coverage, respectively. Adsorption at elevated temperature reduces the substrate as indicated by a strong Ti³⁺ shoulder in the XPS Ti 2p_3/2 peak, with up to 15.6% of the total peak area for the (4×1) structure. STM of different coverages adsorbed at 400°C indicates structural features consisting of two single S atoms placed next to each other along the [0 0 1] direction at the position of the in-plane oxygen atoms. The (3×3) and the (4×1) structure are formed by different arrangements of these S pairs.     

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.     

A photoemission study of 4H---SiC(0001)

A photoemission study using synchrotron radiation of the (0001) surface of 4H-SiC is reported. The investigations were concentrated on the (√3 × √3)-R30° and (6√3 × 6√3)-R30° reconstructed surfaces, prepared by resistive heating at a temperature of about 1000°C and 1250°C, respectively. Results from surfaces heated at intermediate temperatures, exhibiting a mixture of these reconstructions, and after heating at a higher temperature, when graphitisation is clearly observed, are also presented. The √3 and 6√3 reconstructed surfaces exhibit characteristic core level and valence band spectra. High resolution core level spectra show unambiguously the presence of surface shifted components in both the Si 2p and C 1s core levels. For the √3 reconstruction, two surface shifted components are observed both in the Si 2p and C 1s level. For the 6√3 reconstruction, the surface region is found to contain a considerably larger amount of carbon. This carbon is found not to be graphitic since surface C 1s components with binding energies different from a graphitic C 1s peak are observed. Graphitisation, as revealed by the appearance of a graphitic C 1s peak, is observed only after heating to a higher temperature than that required for obtaining a well developed 6√3 diffraction pattern.     

Structure investigation of the nitrogen induced Cu(110)−(2 × 3) phase with 180° low energy impact collision ion scattering spectroscopy

The 180° low energy impact collision ion scattering spectroscopy with detection of noble gas neutrals (180°-NICISS) has been used to investigate the nitrogen saturated Cu(110) surface, which is known to exhibit a (2 × 3) diffraction pattern. The nitrogen induced (2 × 3) phase appears to be the result of a surface reconstruction of a new missing row type, in which every third 100 row of Cu atoms of the first layer is missing. The 180° NICISS patterns further indicate within an accuracy of 0.1–0.2 Å, that the double periodicity in the [1 0] direction is not due to the reconstruction of the Cu surface. Its origin has to be found in the arrangement of the N atoms.     

The Si(001) c(4×4) surface reconstruction: a comprehensive experimental study

We have carried out a comprehensive experimental study of the Si(001) c(4×4) surface reconstruction by scanning tunneling microscopy (STM) (at room temperature and elevated temperatures), Auger electron spectroscopy (AES), reflection high-energy electron diffraction (RHEED) and low-energy electron diffraction (LEED). Si(001) samples were kept under ultra-high vacuum (UHV) at around 550°C until the c(4×4) reconstruction appeared. STM contrast of the c(4×4) reconstruction is strongly influenced by electronic effects and changes considerably over a range of bias voltages.

The c(4×4) surface reconstruction is a result of stress which is caused by incorporation of impurities or adsorbates in sub-surface locations. The resulting c(4×4) reconstruction in the top layer is a pure silicon structure. The main structural element is a one-dimer vacancy (1-DV). At this vacancy, second layer Si-atoms rebond and cause the adjacent top Si-dimers to brighten up in the STM image at low bias voltages. At higher bias voltage the contrast is similar to Si-dimers on the (2×1) reconstructed Si(001). Therefore, besides the 1-DV and the two adjacent Si-dimers, another Si-dimer under tensile stress may complete the 4× unit cell. This is a refinement of the missing dimer model.     

InAs wetting layer evolution on GaAs(0 0 1)

The evolution of two-dimensional (2D) strained InAs wetting layers on GaAs(0 0 1), grown at different temperatures by molecular beam epitaxy, was studied by in situ high-resolution scanning tunneling microscopy. At low growth temperature (400 °C), the substrate exhibits a well-defined GaAs(0 0 1)-c(4 × 4) structure. For a disorientation of 0.7°, InAs grows in the step-flow mode and forms an unalloyed wetting layer mainly along steps, but also in part on the terrace. The wetting layer displays some local c(4 × 6) reconstruction, for which a model is proposed. 1.2 monolayer (ML) InAs deposition induces the formation of 3D islands. At a higher temperature (460 °C), the wetting layer is obviously alloyed even at low InAs coverage. The critical thickness of the wetting layer for the 2D-to-3D transition is shifted to 1.50 ML in this case presumably since the strain is reduced by alloying.     

Existence and thermal stability of mono and dihydride phases on Si(1 1 1) and Ge(1 1 1) surfaces: A photoemission study

Based on UPS and XPS investigations, it is concluded that a monohydride phase forms at first on the Si(1 1 1)7 × 7 surface. Upon further hydrogen dosing at room temperature, a dihydride phase develops and superposes to the previously formed monohydride phase. The dihydride phase desorbs completely around 250°C and the monohydride phase at about 550°C. A pure dihydride phase obtained by H adsorption cannot be observed on a silicon surface. Silane or disilane adsorption at room temperature exhibits the characteristic features of the dihydride phase without the associated monohydride phase. The obtained phase desorbs at the same temperature as the H induced dihydride phase. That is to our mind the only possibility to obtain a pure dihydride phase.

For germanium in careful conditions we observe only a monohydride phase which desorbs at 150°C. For high hydrogen exposures, we obtain a new phase but XPS measurements indicate oxygen contamination. This place desorbs at 225°C and allows clear distinction between H adsorption and contamination. It is concluded that Ge and Si surfaces have different reactivities for hydrogen adsorption. These conclusions are extended to all Ge and Si surfaces either crystallized or amorphous.     

Structure of the Si(011)-(16 × 2) surface and hydrogen desorption kinetics investigated using temperature-programmed desorption

D₂ temperature-programmed desorption (TPD) was used to probe the structure of the Si(011)-(16 × 2) surface. Deuterium was adsorbed at 200°C to coverages θ_D ranging up to complete saturation (approximately 1.1 ML) and the sample heated at 5°C s⁻¹. TPD spectra exhibited three second-order desorption peaks labelled β₂, β*₁ and β₁ centered at 430, 520 and 550°C. Of the proposed models for the Si(011)-(16 × 2) reconstruction, the present TPD results as a function of θ_D provide support for the adatom/dimer model with the β₂ peak assigned to D₂ desorption from the dihydride phase, while the β*₁ and β₁ peaks arise from adatom and surface-atom monohydride phases.     

Defect versus nanocrystal luminescence emitted from room temperature and hot-implanted SiO2 layers

Silicon nanocrystals have been synthesized in SiO₂ matrix using Si ion implantation. Si ions were implanted into 300-nm-thick SiO₂ films grown on crystalline Si at energies of 30–55 keV, and with doses of 5×10¹⁵, 3×10¹⁶, and 1×10¹⁷ cm⁻². Implanted samples were subsequently annealed in an N₂ ambient at 500–1100°C during various periods. Photoluminescence spectra for the sample implanted with 1×10¹⁷ cm⁻² at 55 keV show that red luminescence (750 nm) related to Si-nanocrystals clearly increases with annealing temperature and time in intensity, and that weak orange luminescence (600 nm) is observed after annealing at low temperatures of 500°C and 800°C. The luminescence around 600 nm becomes very intense when a thin SiO₂ sample is implanted at a substrate temperature of 400°C with an energy of 30 keV and a low dose of 5×10¹⁵ cm⁻². It vanishes after annealing at 800°C for 30 min. We conclude that this luminescence observed around 600 nm is caused by some radiative defects formed in Si-implanted SiO₂.     

Highly stable passivation of a Si(1 1 1) surface using bilayer-GaSe

As a stable and ‘epitaxial’ passivation of a Si surface, we propose the bilayer-GaSe termination of a Si(1 1 1) surface. This surface is fabricated by depositing one monolayer of Ga on a clean Si(1 1 1) surface and subsequent annealing in a Se flux at around 520 °C, which results in unreconstructed 1×1 termination of the Si(1 1 1) surface by bilayer-GaSe. We found by scanning tunneling microscopy observation that slow cooling of the clean Si(1 1 1) surface from 850 to 520 °C with simultaneous deposition of a Ga flux results in better termination of the Si(1 1 1) surface. It was also found that this surface is stable against heating around 400 °C in O₂ atmosphere of 3×10⁻³ Pa. By utilizing these properties of the bilayer-GaSe terminated surface, we have succeeded in fabricating ZnO quantum dots on this substrate.     

Surface structures of S/Ni(111) in (√3 × √3 )R30° and (5√3 × 2) phases studied by surface extended X-ray absorption fine structure spectroscopy

The local surface structures of S/Ni(111) in the ( √3 × √3) R30° and (5√3 × 2) phases have been investigated by means of polarization-dependent sulfur K-edge surface EXAFS. In the (√3 × √3 ) R30° phase, sulfur adatoms are found to occupy threefold hollow sites with a S---Ni distance of 2.13 Å and an inclination angle ω of the Sz.sbnd;Ni bonds at 44° from the surface plane. In contrast, in the (5√3 × 2) phase, it is determined that the Sz.sbnd;Ni bond is longer, 2.18 Å, more inclined, ω = 31°, and that the coordination number is not 3 but 4. These results strongly support a picture involving reconstruction of the top nickel layer to form a rectangular structure. Consideration of several models proposed for the (5√3 × 2) phase leads to one which is compatible with both the present results and results recently reported using STM.     

Surface reconstructions and phase transitions on the GaAs(111)B surface

The (111)B surface of GaAs has been investigated using scanning tunneling microscopy (STM) and a number of different reconstructions have been found at different surface stoichiometries. In accordance with electron diffraction studies, we find the series (2 × 2), (1 × 1)_LT, ( ) and (1 × 1)_HT with increasing annealing temperature, corresponding to decreasing surface As concentration. The (1 × 1)_LT is of particular interest, since it only occurs in a narrow temperature window between the two more established reconstructions, the (2 × 2) and the ( ). We find the (1 × 1)_LT to take the form of a mixture of the local structures of both the (2 × 2) and ( ) phases, rather than having a distinct structure. This is behaviour consistent with a kinetically limited system, dominated by the supply of As adatoms to the surface, and may be an example of a continuous phase transition. Above the (1 × 1)_LT transition, atomic resolution images of the ( ) surface reveal only a three-fold symmetry of the hexagonal structural units, brought about by inequivalent surface bonding due to the 23.4° rotation of the surface unit cell relative to the substrate. This is responsible for the disorder found in the ( ) reconstruction, since the structure may form in one of two domains. At lower surface As concentration, the (1 × 1)_HT surface adopts a structure combining small domains of a 19.1° structure and random disorder. There is no apparent similarity between the (1 × 1)_LT and (1 × 1)_HT structures, which may be due to our measurements being conducted at room temperature and without an As flux to control the surface As concentration.     

In situ monitoring of the c( 4 × 4) to the 2 × 4 surface phase transformation on GaAs(001) by grazing incidence X-ray diffraction

The transition between the arsenic saturated c(4 × 4) and the As stabilised 2 × 4 reconstructed GaAs(001) surfaces has been followed in situ on a UHV grazing incidence X-ray diffractometer stage. X-ray diffraction lines specific of either structure have been recorded as a function of temperature. The intensity and lineshape evolution has enabled to propose a model for the transformation involving a homogeneous disordering of the c(4 × 4) surface through random As desorption followed by nucleation and growth of 2 × 4 domains. Under UHV conditions, the irreversible transition is observed over a temperature interval ranging from 330°C to 380°C.     

The effects of hydrogen dose and thermal treatment on the formation of microsplits in hydrogen implanted GaAs

Transmission electron microscopy has been used to study the effect of thermal treatment on the formation of microsplits and damage rafts in hydrogen implanted (1 × 10¹⁶ and 5 × 10¹⁶ H⁺ cm^-2) and annealed (700 and 800°C) GaAs. The results show that microsplit and damage raft formation in implanted samples may be prevented if the samples are first given a pre-anneal heat treatment for 15 minute intervals at 300, 350, 400 and 450°C, during which the hydrogen concentration is reduced without allowing vacancy coalescence to take place.     

Single crystal RuO2/Ti and RuO2/TiO2 interface: LEED, Auger and XPS study

The interactions at the evolving RuO₂/titanium interface have been studied by LEED, AES and XPS. Titanium films of up to 5 monolayers were evaporated onto well ordered and ion sputtered ruthenium dioxide crystal surfaces of (110) and (100) orientation. Stabilization of the surface oxygen content under thermal treatment in UHV (up to 600°C) with increasing titanium coverage was established. After extended (up to 4 h) annealing in O₂ at 600°C an epitaxial ordering of TiO₂ on RuO₂(110) was observed. The (1 × 1) LEED patterns from the epitaxial layer exhibit a reduced background level when compared to the RuO₂ substrate itself. These findings are correlated with the XPS data and are interpreted in connection with the disappearance of the defect RuO₂ phase in the surface layer of the RuO₂. The appearance of the (1 × 2) surface reconstruction at the RuO₂(100)/Ti interface is discussed in the context of maximum cation coordination by oxygen atoms.     

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.     

Reversible H2 passivation of Si ≡ Si3 interface defects in (1 1 1)Si/SiO2

K-band electron spin resonance (ESR) at 4.3 K has revealed the dipole-dipole (DD) interaction effects between [1 1 1]P_b centers (^*Si ≡ Si₃ defects with unpaired sp³ hybrid [1 1 1]) at the 2 dimensional (1 1 1)Si/SiO₂ interface. This has been enabled by the perfectly reversible H₂ passivation of P_b, which affects the defect's spin state. Sequential hydrogenation at 253–353°C and degassing treatments in high vacuum at 743–835°C allowed to vary the P_b density in the range 5 × 10¹⁰ < [P_b] (1.14 ± 0.06) × 10¹³ cm^-2. With increasing [P_b] fine structure doublets are clearly resolved. It is found that (1 1 1)Si/SiO₂ interfaces, dry thermally grown at ≈920°C, naturally comprise a ^*Si ≡ Si₃ defect density — passivated or not — of 1.14 × 10¹³ cm^-2.