The epitaxial growth of Pd electrodeposition on Au(1 0 0) studied by LEED and RHEED

The epitaxial growth of Pd adlayers electrochemically deposited onto Au(1 0 0) has been studied by LEED, RHEED and AES. For the first 6 ML, the Pd deposits grow pseudomorphically on Au(1 0 0) with a lateral expansion of 4.5% with respect to bulk Pd. The strain in the expanded commensurate (1 × 1) Pd layers on Au(1 0 0) begins to be relieved at the Pd coverage between 6 and 9 ML range by formation of a compressed Pd film with respect to Au(1 0 0) surface and the compression increases continuously with thickness. At ca. 20 ML Pd the lattice constant of the film approaches to the bulk Pd and three-dimensional Pd islands develop since around 30 ML coverage. No superstructure due to the Pd-Au surface alloy can be found for coverages from monolayer up to 30 ML Pd on Au(1 0 0). A c(2 × 2) phase has been observed on the Pd-deposited Au(1 0 0) electrodes, which is ascribed to an ordered Cl adlayers adsorbed on Pd adlayers rather than a Pd-Au surface alloy.     

Anisotropic kinetics on growing Ge(0 0 1) surfaces

Reflection high-energy electron diffraction (RHEED), reflectance difference spectroscopy (RDS), and scanning tunneling microscopy (STM) have been used to study the anisotropic kinetics on the growing Ge(0 0 1) surface. While switching of dimer direction in alternate (2 × 1)/(1 × 2) layers causes the bilayer-period oscillations in RD response, RHEED oscillations are governed by variations in surface step densities. We show that the RHEED oscillations are strongly affected by the growth front morphology: when the growth front becomes distributed over several layers, the transition from bilayer- to monolayer-period occurs in RHEED oscillations.     

Growth of Co nanoparticles on a nanostructured θ-Al2O3 film on CoAl(1 0 0)

We have investigated the growth of Co nanoparticles on θ-Al₂O₃/CoAl(1 0 0) by means of Auger electron spectroscopy (AES), high-resolution electron energy loss spectroscopy (EELS), low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). Due to Volmer-Weber growth, Co forms particles with a mean diameter of approximately 2.5 nm and height of 0.8 nm. Even on the entirely covered oxide, there is no Ostwald ripening and Co particles stay structurally isolated. The nanoparticles exhibit a small size distribution and tend to form chains, as predetermined by the streak structure of the oxide template. For sufficient high coverages Co-core-CoO-shell nanoparticles may be evidenced, which is explained as a result of surfactant oxygen. The nanostructured particles may open the door to numerous applications, such as in catalysis and magnetoelectronic applications, where large areas of ordered nanodots are desired.     

Growth and structure of vanadium oxide on anatase (1 0 1) terraces

The interaction of vanadium oxide with epitaxial anatase films exposing (1 0 1) terraces was characterized. The TiO₂ films were grown on vicinal LaAlO₃ (1 1 0) substrates by oxygen plasma-assisted molecular beam epitaxy (OPA-MBE); reflection high energy and low energy electron diffraction (RHEED and LEED) indicated that the films exposed (1 0 1) terraces of the anatase TiO₂ polymorph. When a vanadium oxide monolayer was deposited onto the anatase surface by OPA-MBE at 725 K, only (1 × 1) RHEED and LEED patterns were observed. The V X-ray photoelectron spectroscopy (XPS) peak intensities indicated that the monolayer wetted the anatase surface and so the diffraction patterns were attributed to an epitaxial vanadia layer. Analysis of the vanadium oxide monolayer by X-ray and ultraviolet photoelectron spectroscopies revealed that the V was predominantly 5+. When the vanadia coverage was increased at 725 K, Auger electron spectra showed only very slow attenuation of the anatase Ti peaks while spots began to develop in RHEED patterns recorded along the LaAlO₃ direction; both indicative of 3-D cluster formation. In the orthogonal direction, the RHEED patterns showed unusual diagonal streaks. Meanwhile, the (1 × 1) LEED pattern persisted even after 30 nm of vanadia was deposited. This was attributed to gaps between the 3-D clusters exposing the epitaxial monolayer. Core level XPS spectra of the 3-D clusters revealed a broad V 2p_3/2 peak that was centered at the position expected for V⁴⁺ but could be deconvoluted into three peaks corresponding to V³⁺, V⁴⁺, and V⁵⁺. It is shown that crystallographic shear that accommodates such variations in the oxygen content of V oxides can lead to the diagonal streaks in RHEED patterns recorded along the LaAlO₃ [0 0 1] direction even as the pattern in the orthogonal direction shows sharp transmission spots. The results show that vanadia growth on anatase (1 0 1) proceeds through the Stranski-Krastanov mode with a strong vanadia-titania interaction stabilizing a dispersed vanadia monolayer. The results are compared with previous data for vanadia growth on anatase (0 0 1) where smooth, epitaxial VO₂ films grow ad infinitum.     

Influence of the surface-termination of hexagonal SiC(0 0 0 1) on the temperature dependences of Ge growth modes and desorption

With the aim of comparing initial Ge adsorption and desorption modes on different surface terminations of 4H-SiC(0 0 0 1) faces, 3 × 3, √3×√3R30° (R3) and 6√3×6√3R30° (6R3) reconstructions, of decreasing Si surface richness, have been prepared by standard surface preparation procedures. They are controlled by reflection high energy electron diffraction (RHEED), low energy electron diffraction and photoemission. One monolayer of Ge has been deposited similarly at room temperature on each of these three surfaces, followed by the same set of isochronal heatings at increasing temperatures up to complete Ge desorption. At each step of heating, the structural and chemical status of the Ge ad-layer has been probed. Marked differences between the Si- (3 × 3 and R3) and C-rich (6R3) terminations have been obtained. Ge wetting layers are only obtained up to 400 °C on 3 × 3 and R3 surfaces in the form of a 4 × 4 reconstruction. The wetting is more complete on the R3 surface, whose atomic structure is the closest to an ideally Si-terminated 1 × 1 SiC surface. At higher temperatures, the wetting layer stage transiets in Ge polycrystallites followed by the unexpected appearance on the 3 × 3 surface of a more ordered Si island structure. It denotes a Si clustering of the initial Si 3 × 3 excess, induced by the presence of Ge. A phase separation mechanism between Si and Ge prevails therefore over alloying by Ge supply onto a such Si-terminated 3 × 3 surface. Conversely, no wetting is obtained on the 6R3 surface and island formation of exclusively pure Ge takes place already at low temperature. These islands exhibit a better epitaxial relationship characterized by Ge(1 1 1)//SiC(0 0 0 1) and Ge〈1 1 −2〉//SiC〈1 −1 0 0〉, ascertained by a clear RHEED spot pattern. The absence of any Ge-C bond signature in the X-ray photoelectron spectroscopy Ge core lines indicates a dominant island nucleation on heterogeneous regions of the surface denuded by the 6R3 graphite pavings. Owing to the used annealing cycles, the deposited Ge amount desorbs on the three surfaces at differentiated temperatures ranging from 950 to 1200 °C. These differences probably reflect the varying morphologies formed at lower temperature on the different surfaces. Considering all these results, the use of imperfect 6R3 surfaces appears to be suited to promote the formation of pure and coherent Ge islands on SiC.     

Initial stages of MnAs/GaAs(0 0 1) epitaxy studied by RHEED azimuthal scans

We study the nucleation phase of molecular beam epitaxy of (hexagonal) MnAs on (cubic) GaAs (0 0 1) using reflection high-energy electron diffraction (RHEED) azimuthal scans. The nucleation proceeds from a non-reconstructed initial stage through randomly oriented small nuclei and two orientation stages to the final single-phase epitaxial orientation. The fascinatingly complex nucleation process contains elements of both Volmer-Weber and Stranski-Krastanov growth. The measurement demonstrates the potential of high-resolution RHEED techniques to assess details of the surface structure during epitaxy.     

Pd, Co and Co-Pd clusters on the ordered alumina film on NiAl(1 1 0): Contact angle, surface structure and composition

We have investigated the structure and morphology of Co and Pd clusters grown at room temperature on an alumina film on NiAl(1 1 0) by scanning tunneling microscopy, low energy ion scattering and Auger electron spectroscopy. We have also studied the clusters after annealing to 300 °C and Pd clusters deposited at 300 °C. Mixed Co-Pd clusters obtained by sequential deposition at room temperature were also studied. Pure Co deposited at room temperature forms a single type of clusters, most or all of them with close-packed planes parallel to the oxide surface. Their shape can be approximated by truncated spheres with a high contact angle of 115-125°. These clusters are stable upon annealing up to 300 °C.Pd clusters deposited at room temperature grow in two different modes. At the reflection domain boundaries the clusters grow in their thermodynamically favorable shape. The clusters do not have a single crystallographic orientation and their shape can be approximated by a truncated sphere with a high contact angle of about 110°, especially at very low coverages (below 0.05 ML). At the antiphase domain boundaries, the Pd clusters grow in (1 1 1) orientation and on some of them small (1 1 1) facets appear at their tops already at low coverages. For higher coverages of Pd, the majority of Pd clusters are rather flat with a large Pd(1 1 1) facet on top. The clusters’ shape at the antiphase domain boundaries differs from the thermodynamically favorable one, due to kinetic limitations, especially at higher coverages. Annealing the Pd clusters to 300 °C leads to re-structuring of these Pd clusters. They transform into higher and more rounded clusters and a thin disordered alumina film is formed on top of the clusters. When Pd is deposited at 300 °C, about 16% of the Pd clusters have a steep slope and rounded tops. The rest of the Pd forms lower clusters, goes subsurface and is covered by a disordered alumina film. When Co and Pd are deposited sequentially, Pd covers the Co clusters forming a shell. The resulting mixed clusters are still truncated spheres with a lowered contact angle. For deposition in the reverse order (first Pd and then Co) we found that Co forms an alloy with Pd already at room temperature.     

Co on thin Al2O3 films grown on Ni3Al(1 0 0)

The growth of Co on thin Al₂O₃ layers on Ni₃Al(1 0 0) was investigated by Auger electron spectroscopy, high resolution electron energy loss spectroscopy (EELS), and scanning tunneling microscopy. At 300 K, Co grows in three-dimensional clusters on top of the Al₂O₃ layer. A defect structure of the alumina layer plays a crucial role during the early stage of Co growth. After deposition of 10 Å of Co, a complete screening of the dipoles of the Al₂O₃ layer due to the Co film is found in the EELS measurements. Annealing the Co film reveals a process of coalescence of Co clusters and, above 700 K, diffusion of the Co atoms through the oxide film into the substrate takes place.     

Reflection high-energy positron diffraction pattern from a Si(1 1 1)-(7 × 7) surface

We have investigated the feature of reflection high-energy positron diffraction (RHEPD) pattern from a Si(1 1 1)-(7 × 7) surface. The RHEPD pattern observed in the total reflection condition is quite different from the conventional reflection high-energy electron diffraction (RHEED) pattern. This fact is attributed to the different penetration depths of positrons and electrons. We show that the intensity distribution of RHEPD pattern is reproduced considering the dimer-adatom-stacking fault (DAS) model with optimized atomic positions and scattering potentials of adatoms and rest atoms.     

Hydrogen adsorption on GaAs(0 0 1)-c(4 × 4)

Exposure of the As-terminated GaAs(0 0 1)-c(4 × 4) reconstructed surface to atomic hydrogen (H) at different substrate temperatures (50-480 °C) has been studied by reflection high-energy electron diffraction (RHEED) and scanning tunnelling microscopy (STM). Hydrogen exposure at low temperatures (∼50 °C) produces a disordered (1 × 1) surface covered with AsH_x clusters. At higher temperatures (150-400 °C) exposure to hydrogen leads to the formation of mixed c(2 × 2) and c(4 × 2) surface domains with H adsorbed on surface Ga atoms that are exposed due to the H induced loss of As from the surface. At the highest temperature (480 °C) a disordered (2 × 4) reconstruction is formed due to thermal desorption of As from the surface. The results are consistent with the loss of As from the surface, either through direct thermal desorption or as a result of the desorption of volatile compounds which form after reaction with H.     

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.     

A real-time investigation by RHEED of the homoepitaxial growth of GaAs on (0 0 1) oriented surfaces

In this letter we report on the formation of long-range surface disorder features during the growth by molecular beam epitaxy (MBE) of homoepitaxial GaAs (0 0 1) films having the β2(2 × 4) reconstruction. Observations were made in real-time at the growth temperature using reflection high energy electron diffraction (RHEED) and analyzed kinematically. We show that kinks (cooperative shifts of whole columns of 2 × 4 units along the [1 1 0] direction) form rapidly as growth commences and that the antiphase domain structure present on the substrate prior to growth as a result of the arrangement of As-As dimers persists. This produces a surface with two types of long-range disorder. We speculate on the role of incident Ga atoms on this process.     

Adsorption of glycine on a NiAl(1 1 0) alloy surface

The adsorption and desorption of glycine (NH₂CH₂COOH), vacuum deposited on a NiAl(1 1 0) surface, were investigated by means of Auger electron spectroscopy (AES), low energy electron diffraction (LEED), temperature-programmed desorption, work function (Δφ) measurements, and ultraviolet photoelectron spectroscopy (UPS). At 120 K, glycine adsorbs molecularly forming mono- and multilayers predominantly in the zwitterionic state, as evidenced by the UPS results. In contrast, the adsorption at room temperature (310 K) is mainly dissociative in the early stages of exposure, while molecular adsorption occurs only near saturation coverage. There is evidence that this molecularly adsorbed species is in the anionic form (NH₂CH₂COO⁻). Analysis of AES data reveals that upon adsorption glycine attacks the aluminium sites on the surface. On heating part of the monolayer adsorbed at 120 K is converted to the anionic form and at higher temperatures dissociates further before desorption. The temperature-induced dissociation of glycine (<400 K) leads to a series of similar reaction products irrespective of the initial adsorption step at 120 K or at 310 K, leaving finally oxygen, carbon and nitrogen at the surface. AES and LEED measurements indicate that oxygen interacts strongly with the Al component of the surface forming an “oxide”-like Al-O layer.     

Variety of iron silicides grown on Si(0 0 1) surfaces by solid phase epitaxy: Schematic phase diagram

We systematically studied the formation of various iron-silicide phases, grown on Si(0 0 1) surfaces by solid phase epitaxy, with scanning tunneling microscopy, low-energy electron diffraction and reflection high-energy electron diffraction. We found and studied the phases of c(2 × 2) islands, rectangle-like islands, elongated islands, layered islands, dome-like islands, eddy and cracked structures, and small clusters. A schematic phase diagram of these phases is successfully summarized against iron coverage at room temperature and subsequent annealing temperature.     

Ultra-thin film growth of titanium dioxide on W(1 0 0)

We have employed low energy electron diffraction (LEED) and X-ray photoelectron spectroscopy to follow the epitaxial growth of thin films of TiO₂ on W(1 0 0). The films were grown both by metal vapour deposition of titanium onto the substrate in UHV with subsequent annealing in a low partial pressure of oxygen, and by metal vapour deposition in a low partial pressure of oxygen. LEED patterns showed the characteristic patterns of (1 1 0) oriented rutile. A systematic spot splitting was observed and attributed to a stepped surface. The calculated step height was found to be in good agreement with that expected for rutile TiO₂(1 1 0), 3.3 Å. Titanium core level shifts were used to identify oxidation states as a function of film thickness allowing the interpretation in terms of a slightly sub-stoichiometric interface layer in contact with the substrate. In combination with the LEED patterns, the film structure is therefore determined to be (1 1 0) oriented rutile with a comparable level of stoichiometry to UHV prepared bulk crystals. The ordered step structure indicates considerable structural complexity of the surface.     

Texture of molybdenum thin films on SrTiO3(1 0 0): A RHEED study

The structure of ultrathin Mo films on SrTiO₃(1 0 0) was studied by in situ reflection high-energy electron diffraction (RHEED). A different structure was observed for films less than 20 Å thick than for thicker films. These films were epitaxial and had a metastable structure. Thicker films had the dimensions of equilibrium bcc Mo(1 1 0). Relaxation processes transformed the metastable Mo into bcc Mo, resulting in the following orientation relationships between Mo and SrTiO₃: (1 1 0)[0 0 1]_bcc Mo ∥ (1 0 0)[0 0 1]_SrTiO3 and (1 1 0)[1 1 1]_bcc Mo ∥ (1 0 0)[0 1 1]_SrTiO3. The formation of such specific orientations is related to transformations via the Bain and Needle Path, respectively.     

Phase discrimination of iron-silicides on Si(0 0 1) surfaces by three-dimensional reciprocal-lattice mapping

Various iron-silicides are grown on clean Si(0 0 1) surfaces by solid phase epitaxy, a process which involves the deposition of iron and subsequent annealing [6]. Among them, we studied the structure of three-dimensional (3D) elongated islands, which are the major silicide type produced at lower Fe coverage (∼1 monolayer) and ?500-600 °C annealing. We applied a newly developed method of azimuth-scan reflection high-energy electron diffraction (RHEED) to obtain 3D reciprocal-lattice mapping. We succeeded in discriminating an α-FeSi₂ phase from controversial bulk phases of the islands, and we were also able to determine the orientation relation as and , where the lattice mismatches are −1% in direction and +34% in direction. The attenuation of the incident electron beam along the length direction of the islands leads to extremely weak spots in the RHEED pattern. We emphasize that such an analysis of the reciprocal-lattice mapping is also useful in studying other 3D island structures. Using scanning tunneling microscopy, we showed that the island’s elongated directions are perpendicular to the dimer rows of the substrate located under the islands. The islands are located near the S_B step edges. The elongation lengths of the islands are almost the same as the widths of the Si substrate terraces. We discussed the formation mechanism of the 3D-elongated islands. From an atomic image of the facet and edge of a 3D-elongated island, we proposed an atomic-structure model of the island facet and edge: a Si adatom on the hollow site of four Si atoms of an unit, with ordering in the direction of the elongation, forming an facet locally.     

Adsorption of Pb on NiAl(1 1 0): energetics and structure

The adsorption of Pb onto a NiAl(1 1 0) single crystal surface at 300 K has been studied by Auger electron spectroscopy (AES), Low energy electron diffraction (LEED), molecular beam/surface scattering and single crystal adsorption calorimetry (SCAC). AES indicates a Stranski-Krastanov growth mode, i.e., Pb initially grows on NiAl(1 1 0) two-dimensionally until the first layer completes at 0.89 ML, where a superstructure is observed by LEED, followed by 3D islanding. Measurements of the Pb gas that does not stick indicate that Pb sticks on NiAl(1 1 0) with an initial probability of 0.99. The initial heat of adsorption of Pb on NiAl(1 1 0) is 249 ± 10 kJ/mol. Due to the repulsive interactions between Pb adatoms, the heat of adsorption decreases within the first layer to a value identical to the heat of sublimation of bulk Pb (195 kJ/mol), where it remains at higher coverages. This first application of adsorption calorimetry on such a thick sample (75 μm versus 0.2-8 μm previously) demonstrates that adsorption calorimetry can be extended to a wider range of surfaces, since this thickness can be achieved with nearly any single crystal material by simple mechanical thinning.     

Epitaxial growth of MnO/Ag(0 0 1) films

Among the 3d transition metal monoxides, MnO plays a particular role due to the high spin ground state of the 3d⁵ configuration of Mn²⁺. Therefore, MnO could be an excellent model system to investigate many kinds of spin dependent or magnetic interactions between electrons in the surface of an antiferromagnetic solid. But in practice, most experimental investigations on crystalline MnO(0 0 1) surfaces suffer from the bad structural quality of the surface of cleaved bulk crystals. In this paper, we report on the epitaxial growth of MnO/Ag(0 0 1) surfaces, which is proved to be a method to produce crystalline MnO(0 0 1) surfaces of high structural order.