Structure of high-index GaAs surfaces – the discovery of the stable GaAs (2 5 11) surface

We present a brief overview of surface structures of high-index GaAs surfaces, putting emphasis on recent progress in our own laboratory. By adapting a commercial scanning tunneling microscope (STM) to our molecular beam epitaxy and ultra high vacuum analysis chamber system, we have been able to atomically resolve the GaAs( )B (8 ×1), (114)Aα2(2×1), (137), (3 7 15), and (2 5 11) surface structures. In cooperation with P. Kratzer and M. Scheffler from the Theory Department of the Fritz-Haber Institute we determined the structure of some of these surfaces by comparing total-energy calculations and STM image simulations with the atomically resolved STM images. We present the results for the {112}, {113}, and {114} surfaces. Then we describe what led us to proceed into the inner parts of the stereographic triangle and to discover the hitherto unknown stable GaAs (2 5 11) surface. Received: 16 May 2001 / Accepted: 23 July 2001 / Published online: 3 April 2002     

Electron diffraction at stepped homogeneous and inhomogeneous surfaces

Defect analysis at surfaces with LEED or RHEED have so far been essentially restricted to steps or superstructure domains. Even if there are no superstructures, variations of the scattering factor influence the spot profile. With the now available high-resolution instruments more details of the spot profile may be observed. Therefore it will be discussed how a careful study of the spot profile at different energies may be used to analyze a surface with simultaneous steps and inhomogeneities. It will be shown how the asperity height is obtained without fitting parameters and how inhomogeneities are analyzed with respect to coverage and size distribution.     

SPA-LEED studies of growth of Ag on Ag(111) at low temperatures

The surface morphology after deposition of Ag on Ag(111) at low temperatures (130–200 K) has been studied in detail with SPA-LEED (Spot-Profile Analysis of Low-Energy Electron Diffraction). The surface roughness and the mean terrace size have been quantitatively determined under various conditions. At 130 K the surface roughness increases with coverage exactly according to the relation = ^1/2, which indicates that the inter-layer diffusion can be neglected at 130 K. Although the mean terrace length decreases with increasing coverage (following an approximate power law of ^–2/3) for all studied coverages, it is much larger than expected for a pure random or Poisson-growth mode without any diffusion of the adatoms. Therefore, Ag grows on Ag(111) at this temperature without interlayer diffusion but with intra-layer diffusion. The intralayer diffusion barrierE _d has been determined by measuring the temperature dependence of the two-dimensional island density according to the nucleation theory (supposing a critical nucleus size of one). The obtained valueE _c=0.18 eV agrees with the theoretical calculations and previous measurements. Furthermore, from comparing measured and Monte-Carlo-simulated (MC) surface roughness at different deposition temperatures we obtain E=0.05 eV as a lower limit for the additional barrier at steps.     

Effects of nearest and next-nearest neighbour interaction parameters on atomic correlation functions of stepped surfaces

We extend the range of the interaction between the surface scatterers to the next-nearest neighbours and thus treat the stepped surface as a second-order Markov chain. We employ two interaction parameters to describe the behaviour of the atomic pair correlation function for a two-level system and derive an exact expression for this function. This expression is then used to calculate the profile of the diffracted intensity. The effects of the interaction parameters on the intensity profiles as well as on the terrace width distributions are investigated in detail and compared to the molecular beam epitaxy measurement of Si on a Si(111) surface. The physical meaning of the interaction parameters is also interpreted in terms of the Ising model.     

Analyses of HF/NH4F buffer-treated Si(111) surfaces using XPS,REM and SIMS

The effect of different cleaning procedures on Si(111) wafers has been studied. A three-step cleaning process was used. The first two steps (thermal oxidation followed by RCA cleaning) were common to all samples. The final step involved rinsing in one of a set of HF/NH4F buffer solutions with a wide range ofpH values. Three different surface techniques were used for characterizing the chemical condition and morphology of the treated surfaces: XPS (X-ray Photoemission Spectroscopy), REM (Reflection Electron Microscopy) and SIMS (Secondary-Ion Mass Spectroscopy). It has been found that thepH value of an HF solution does significantly affect the etching rate and morphology of the Si(111) surface: For the same type of solution, the smaller thepH value, the higher the etching rate. Basic solutions withpH values larger than eight have a much weaker etching effect on the surface, which is contradictory to some previous reports. The most effective solutions for the etching of the Si(111) surface are the solutions of HF buffered by NH₄F, with thepH in the range of 2–6. REM images indicate that the surface morphology after etching in the HF solution is strongly affected by the length of the etching time: Overetching will roughen the surface. The SIMS data show that water rinsing in air during the cleaning process does speed up oxidation, but it is necessary to use water to clean off the residuals from the HF solutions.     

Morphology, bond saturation and reconstruction of hexagonal SiC surfaces

Received: 21 March 1997     

Surface phase diagram and temperature induced phase transitions of Sn/Cu(1 0 0)

Room temperature deposition of Sn on Cu(1 0 0) gives rise to a rich variety of surface reconstructions in the submonolayer coverage range. In this work, we report a detailed investigation on the phases appearing and their temperature stability range by using low-energy electron diffraction and surface X-ray diffraction. Previously reported reconstructions in the submonolayer range are p(2 × 2) (for 0.2 ML), p(2 × 6) (for 0.33 ML), ()R45° (for 0.5 ML), and c(4 × 4) (for 0.65 ML). We find a new phase with a structure for a coverage of 0.45 ML. Furthermore, we analyze the temperature stability of all phases. We find that two phases exhibit a temperature induced reversible phase transition: the ()R45° phase becomes ()R45° phase above 360 K, and the new phase becomes p(2 × 2) also above 360 K. The origin of these two-phase transitions is discussed.     

New reconstruction-stoichiometry correlation for GaAs(0 0 1) surface treated by atomic hydrogen

The structure, stoichiometry and electronic properties of the GaAs(0 0 1)-(2 × 4)/c(2 × 8) surface treated by cycles of atomic hydrogen (AH) exposure and subsequent annealing in UHV were studied with the aim of preparing the Ga-rich surface at low temperatures. Low energy electron diffraction showed reproducible structural transformations in each cycle: AH adsorption at the (2 × 4)/c(2 × 8) surface led to the (1 × 4) structure at low AH exposure and to a (1 × 1) surface at higher AH exposure with subsequent restoration of the (2 × 4)/c(2 × 8) structure under annealing at 450 °C. The cycles of AH treatment preserved the atomic flatness of the GaAs(1 0 0) surface, keeping the mean roughness on to about 0.15 nm. The AH treatment cycles led to the oscillatory behavior of 3dAs/3dGa ratio with a gradual decrease to the value characteristic for the Ga-rich surface. Similar oscillatory variations were observed in the work function. The results are consistent with the loss of As from the surface as a result of the desorption of volatile compounds which are formed after reaction with H. The prepared Ga-rich GaAs(0 0 1) surface showed the stability of the (2 × 4)/c(2 × 8) structure up to the annealing temperature of 580 °C.     

Free energies of steps on (111) fcc surfaces

For a hexagonal two-dimensional lattice we derive, using a surprisingly simple route, exact expressions for the step free energies along the high symmetry directions, 〈1-10〉 and 〈11-2〉. If we consider only nearest-neighbor interactions, ε, and ignore step overhangs the step free energy vanishes at a temperature . In a more sophisticated model that incorporates step overhangs we find a reduction of T_R to about 0.87ε/k_b. The obtained step free energy expressions are also valid for the free energy of walls between two regions of opposite spins of the triangular 2D Ising system.     

Isothermal adsorption kinetics on heterogeneous surfaces

Adsorption kinetics on energetically heterogeneous surfaces under isothermal conditions is analyzed using the uniform energy distribution model. Considering the quasi-equilibrium of surface diffusion between the adsorption sites with different energy, the kinetic equations dΘ/dt=(k_ap−A_dK_diff)(1−Θ) for first-order adsorption and dΘ/dt=k_ap(1−Θ)²−A_dK_diffΘ(1−Θ) for dissociative adsorption are obtained, where K_diff is a coefficient describing the surface diffusion equilibrium, which depends on the coverage and the energy distribution. Under isochoric conditions with p decreasing due to adsorption, surface diffusion accelerates the rate towards equilibrium significantly, as observed in static calorimetric adsorption experiments. An approximate solution in Lagergren form is derived for this condition.     

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.     

Phase transitions in metals on metals

Phase transitions in two-dimensional metal layers on metal surfaces are discussed, with emphasis on systems with attractive lateral interactions on densely packed surfaces. The experimental tools which give information on these transitions are described briefly and the results obtained with them are illustrated by examples of various metals on W and Mo surfaces.     

Effect of Bi surfactant on the heteroepitaxial growth in Fe/Cr(100) multilayers

This study was to investigate the surfactant effect of Bi on the heteroepitaxial growth of Fe/Cr(100) multilayers by reflection high-energy electron diffraction (RHEED) measurements. With predeposition of submonolayer Bi on Fe(100) prior to evaporation of Fe/Cr multilayer, more long-lasting RHEED intensity oscillations were observed. This implies that the layer-by-layer growth of Fe/Cr multilayer is enhanced. The observations of grazing incidence X-ray reflectivity confirmed that the interface structures of Fe/Cr multilayer with Bi were sharper than that of multilayer without Bi. The study was also to investigate the magnetotransport properties between Bi surfactant-mediated multilayers and normal ones. The magnetoresistance (MR) ratio of the multilayers was enhanced by predeposition of Bi.     

Towards an understanding of surfactant action in the epitaxial growth of metals: The case of Sb on Ag (111)

We address the role of surfactant adsorbates in determining changes in the homoepitaxial growth mode of metals, discussing the case of Sb on Ag (111). From ab initio calculations, we extract evidence that the mechanism operative in this system is that Sb induces an irregular shape and an increase in density of the growing Ag islands, and an ensuing increase of the number of attempts for an adatom to descend to a lower terrace. This results from a combination of peculiar properties of this system: Sb is adsorbed insubstitutional surface sites, leading to the formation of a Sb–Ag surface alloy; deposited Ag has reduced mobility on Sb-covered Ag (111), from which follows a higher nucleation probability. The island shape is irregular since the surface alloy is disordered. Surface seggregation of Sb once the growing layer is completed furthers the phenomenon for many deposited Ag layers. Our explanation of the surfactant action of Sb on Ag (111) does not require a reduction of the downstep diffusion barrier, which may, however, be a concurrent factor helpful to interlayer mass transport and layerby-layer growth.     

The application of RHEED intensity effects to interrupted growth and interface formation during MBE growth of GaAs/(Al,Ga)As structures

There is a diffraction-induced phase effect in the RHEED intensity oscillation technique used in MBE, whereby intensity maxima only correspond to monolayer completion for very restricted conditions. In particular, the angle of incidence of the primary beam is extremely critical. The effect occurs because the total intensity at the measured position of the specular beam is always derived from at least two different diffraction processes, which do not have the same phase relation to monolayer formation. It can be accomodated either by a systematic series of measurements to establish an empirical relationship between incidence angle and phase, or by Fourier transform techniques. Unless full account is taken of this purely diffraction-induced effect, very misleading results can be obtained for the time constants of the recovery period following cessation of growth and this is illustrated for GaAs. The effect also has important implications for the growth-interrupt technique. In addition, it is shown that for heterojunction formation in the GaAs/(Al, Ga)As system, adatom (Ga and Al) migration lengths are of greater importance than the position in the monolayer at which the composition is changed, and that RHEED can provide only limited information on the interface structure.     

Sb induced (7×7) to (1×1) surface phase transformation of the Si(111) surface

Adsorption of Sb at a very low flux rate results in an epitaxial layer-by-layer growth on Si(111) surface held at room-temperature. Band-bending is not observed for submonolayer Sb coverages while sharp changes in the photoemission features are observed for 1.0 monolayer (ML) Sb adsorption. Changes in the core level binding energy and width in X-ray photoelectron spectroscopy, surface related feature in Electron energy loss spectroscopy and spot intensity ratios in Low energy electron diffraction studies suggest a surface phase transition upon adsorption of 1.0 monolayer of Sb. A plausible model is proposed to explain the abrupt metal-semiconductor transformation at this critical coverage of 1.0 ML.     

In-situ monitoring of interface formation using the phase shift of reflection high-energy electron diffraction intensity oscillations

A novel phase shift of Reflection High-Energy Electron Diffraction (RHEED) intensity oscillations during heterointerface formation allows direct monitoring of segragation at GaAs/Al _x Ga_1–x As interfaces. The effect should be applicable to other materials systems as it is due to the reconfiguration of the surface structure at the heterointerface.     

Investigation of a new method to control thin-film growth

Results of investigations of a possible application of RHEED azimuthal plots of characterize in situ epitaxially grown thin films are described. Dynamically calculated and measured azimuthal plots for Si(111) are compared. A set of azimuthal plots experimentally collected at different stages of preparation of a Si/YSi_2-x/Si(111)-7×7 layered structure are presented.     

Ice adhesion on super-hydrophobic surfaces

In this study, ice adhesion strength on flat hydrophobic and rough super-hydrophobic coatings with similar surface chemistry (based on same fluoropolymer) is compared. Glaze ice, similar to naturally accreted, was prepared on the surfaces by spraying super-cooled water microdroplets at subzero temperature. Ice adhesion was evaluated by spinning the samples at constantly increasing speed until ice delamination occurred. Super-hydrophobic surfaces with different contact angle hysteresis were tested, clearly showing that the latter, along with the contact angle, also influences the ice-solid adhesion strength.     

Interplay of surface morphology, strain relief, and surface stress during surfactant mediated epitaxy of Ge on Si

Lattice-mismatch-induced surface or film stress has significant influence on the morphology of heteroepitaxial films. This is demonstrated using Sb surfactant-mediated epitaxy of Ge on Si(111). The surfactant forces a two-dimensional growth of a continous Ge film instead of islanding. Two qualitatively different growth regimes are observed. Elastic relaxation: Prior to the generation of strain-relieving defects the Ge film grows pseudomorphically with the Si lattice constant and is under strong compressive stress. The Ge film relieves strain by forming a rough surface on a nm scale which allows partial elastic relaxation towards the Ge bulk lattice constant. The unfavorable increase of surface area is outbalanced by the large decrease of strain energy. The change of film stress and surface morphology is monitored in situ during deposition at elevated temperature with surface stress-induced optical deflection and high-resolution spot profile analysis low-energy electron diffraction. Plastic relaxation: After a critical thickness the generation of dislocations is initiated. The rough phase acts as a nucleation center for dislocations. On Si(111) those misfit dislocations are arranged in a threefold quasi periodic array at the interface that accommodate exactly the different lattice constants of Ge and Si. Received: 1 April 1999 / Accepted: 17 August 1999 / Published online: 6 October 1999