In situ spectroscopic ellipsometry: Application to Sb coverage measurement in the monolayer range on Si (111)

In this paper, we present an analysis of antinomy deposition on silicon in the range of 0.1 to 1 monolayer by in situ spectroscopic ellipsometry. After a careful choice of viewpoint material, ellipsometric measurements are found to be sensitive to small surface perturbations, especially with antimony. In fact, less than a 0.1 monolayer of antimony on silicon at room temperature is detectable. Moreover, a linear dependence of the ellipsometric signal on Sb coverage is observed in the monolayer range. Consequently, the signal versus time variation directly gives the Sb adsorption kinetics on silicon. The saturation to one monolayer of compact antimony on silicon surface is used in order to calibrate the spectra.     

Initial stage of Pd adsorption on Si(111)7 × 7 surface studied by AES and EELS

The initial stage of adsorption of Pd on a Si(111)7 × 7 surface has been studied by means of Auger electron spectroscopy (AES), electron energy loss spectroscopy (EELS) and surface work-function change. For Pd deposition at room temperature (RT) the Si(LVV) Auger signal intensity decays in a broken linear line. The structure factor, defined as the intensity ratio of the subpeak to the main one in Si(LVV) Auger spectra, increases up to a maximum around one monolayer coverages. In EELS spectra two peaks, characteristics of Pd, appear at the completion of the first Pd layer. Pd atoms deposited on Si(111) at RT form initially flat layers of a few monolayers height without mixing with substrate Si atoms. For Pd deposition at a moderately high temperature (MT) of about 300°C, however, the structure factor for Si(LVV) Auger spectra does not change. EELS peaks, characteristic of Si substrate, remain clearly even beyond one monolayer coverage. Pd atoms deposited at MT are unstable and easily diffuse into the bulk. We present evidences to support the “screening” model for the bond-breaking mechanism at the Pd/Si interface.     

The epitaxial growth of thallium on copper (100): A study by LEED,AES, UPS and EELS

LEED, AES, UPS and EELS have been used to observe the growth of thallium in the Stranski-Krastanov mode on copper(100). In the sub-monolayer range, thallium forms three commensurate ordered overlayer structures. The transition from the first overlayer structure to the second involves a transition from a one-dimensional to a two-dimensional structure. The resulting change in co-ordination number reduces the binding energy of the thallium 5d core levels and increases their width.     

An ISS,AES, and CO chemisorption study of titania overlayers on Rh(111)

Ion scattering spectroscopy (ISS), Auger electron spectroscopy (AES) and crystal current measurements have been used to characterize the growth of titania overlayers deposited on a Rh(111) surface. Titania grows two-dimensionally during the first monolayer, with subsequent growth nearly layer-by-layer. The results show agreement among ISS, AES, and crystal current measurements in determination of monolayer coverage. The effect of titania on the chemisorption of CO on Rh(111) has also been investigated and compared with previous studies of titania deposited on Group VIII metals. Temperature-programmed desorption (TPD) of CO shows that titania has relatively little effect on the desorption energy of CO, and that the chemisorption capacity is proportional to the exposed Rh area. The results support a site-blocking model of chemisorption suppression.     

Limitation of Auger electron spectroscopy in the determination of the metal-on-oxide growth mode: Pd on MgO(100)

A discussion on the use of Auger electron spectroscopy as a quantitative tool to determine the growth mode of metals on single crystal oxide surfaces is presented. In the case of Pd grown epitaxially on MgO(100), the three-dimensional character of the growth is easily seen at coverage above one monolayer. However, in the submonolayer regime, and mainly at low substrate temperatures, the AES results are ambiguous. The combination of AES with the more sensitive helium-atom diffraction method allows us to demonstrate that the growth is three-dimensional from the early stages, the particles becoming flatter when the substrate temperature decreases. We compare our results with other growth studies on different metal/oxide systems. At low temperature, the ideal growth modes are not always observed, the final morphology of the films being determined mainly by kinetic effects. Thus a pseudo-Stranski-Krastanov growth mode is often obtained with formation of 2D islands followed by 3D clustering from a critical submonolayer coverage.     

The growth mode of aluminium on silver (111)

The geometric and electronic structures occuring during the growth of Al on a single crystal Ag(111) surface have been studied using a combination of low energy electron diffraction (LEED), Auger electron spectroscopy (AES), energy loss spectroscopy (ELS) and work function measurements. The Auger signal versus deposition time plots, which were used to monitor the growth mode, are shown to behave in an identical fashion to that expected for layer-by-layer (Frank-van der Merwe) growth. LEED was used to determine the lateral periodicity of thin Al films and shows that Al forms, at very small coverages, 2D islands which have the same structure as the Ag(111) substrate and which grow together to form the first monolayer. At substrate temperatures of 150 K a well defined (1 × 1) structure with the same orientation as the underlying Ag(111) can be seen up to at least 12 ML. After completion of the third monolayer the ELS spectrum approached that observed for bulk aluminium. At a coverage of 3 ML the work function decreases by 0.4 eV from the clean silver value.     

Quantitative aspects of Auger electron spectroscopy; On the importance of attenuation of the primary electron beam

Measurements of Auger electron currents at different energies of the primary electrons and at different angles of incidence suggest that attenuation of the primary electron beam in the crystal has a significant influence on the measured Auger currents. This makes it possible to distinguish between a monolayer and a multilayer system, i.e. between impurity atoms in the top atomic layer and impurity atoms dispersed through the surface region. Comparison of AES and ellipsometric measurements of monolayer and multilayer systems on silicon and germanium surfaces shows that AES results can be interpreted to give quantitative information about the number of atoms of the type investigated.     

Initial oxidation process of Mg films characterized by AES,EELS, and UPS

Initial oxidation process of Mg films was investigated by Auger electron spectroscopy (AES), electron energy loss spectroscopy (EELS) and ultraviolet photoelectron spectroscopy (UPS). A polycrystalline Mg film was exposed to oxygen at room temperature. An inspection of EELS reveals that the initial oxidation process could be classified according to the curve profile in the low energy loss region. The oxide formation is initiated after oxygen exposure of 3 L (Langmuir).     

Growth of GaN films on CoGa(001): an EELS and AES study

The formation and properties of ultra-thin GaN films were investigated by means of high-resolution electron energy-loss spectroscopy (EELS) and Auger electron spectroscopy (AES). Using the intermetallic alloy CoGa as the substrate material, GaN can be prepared on the (001) surface upon adsorption of ammonia at 80 K and subsequent thermal decomposition. Ultra-thin GaN films were grown by repeated cycles of ammonia adsorption and heating to 650 K. The GaN films show an FK mode at 695 cm⁻¹, in agreement with calculated spectra based on IR parameters. The electronic energy gap is determined to be E_g ≈ 3.5 eV.     

Iron deposition on the five-fold surface of the icosahedral Al-Pd-Mn quasicrystal

The room temperature adsorption behaviour of Fe on the five-fold surface of i-Al-Pd-Mn has been studied using scanning tunneling microscopy (STM), low energy electron diffraction (LEED), and Auger electron spectroscopy (AES). A complex growth scenario for Fe adsorption on this substrate is observed with STM. At coverages up to about 3 MLE (monolayer equivalent), layer-by-layer growth is observed whereby small clusters and islands are formed which eventually coalesce into almost complete monolayers. No LEED pattern is observed, indicating that the layers are disordered. The AES results rule out intermixing. Above this coverage, there is a transition to a multilayer island growth mode. The islands are rotated by 72° and have the bcc(1 1 0) Fe structure. The results are compared with previous work on Fe adsorption on this substrate and on Al and Fe single crystal substrates.     

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.     

The adsorption of cyclic hydrocarbons on Ru(001): II. Cyclohexane

The adsorption of cyclohexane on Ru(001) at 90 K has been investigated by thermal desorption mass spectrometry, EELS, UV photoemission and LEED. Thermal desorption indicates the adsorption of the undissociated molecule first in a chemisorbed monolayer (T_d = 200 K) with subsequent formation of multilayers (T_d = 165 K) at higher exposures. The vibrational spectrum obtained by EELS is characterized by a frequency shift of the C-H stretching mode from 2920 cm^?1 (multilayer) to 2560 cm^?1 for the chemisorbed monolayer. Off-specular EELS data indicate two different electron scattering mechanisms for the C-H stretching mode. Whereas for the C-H stretching mode of the multilayer, large angle electron impact scattering is observed, the C-H soft-mode of the monolayer is largely due to small angle dipolar scattering. The He I photoelectron spectra of cyclohexane multilayers are characteristic of the undissociated molecule. A new assignment of C(2s) and the lowest C(2p) level, based on a comparison with benzene, shows that the chemisorbed monolayer is characterized by the absence of emission or broadening of the 2a_1u level. This is attributed to C_3v symmetry of the chemisorbed layer and to a possible interaction of the 2a_Iu orbital with the metal surface.     

Sodium adsorption on a Ge(100)-(2 × 1) surface

The adsorption of Na on a Ge(100)-(2 × 1) surface has been studied by means of AES, LEED, EELS, TPD and work-function measurements. In the submonolayer coverage region the coverage dependencies of the desorption activation energy E(Θ) and desorption frequency v(Θ) have been determined using the threshold TPD method. Our experimental data show that after the completion of the first Na layer, 3D crystallites develop on the Na/Ge(100) surface (Stranski-Krastanov growth mode). For Θ > 1 ML, formation, followed by decomposition of a certain Na---Ge surface compound occurs in the temperature range 410–550 K.     

Ellipsometric studies of adsorption reactions on clean surfaces

The ellipsometric effects measured upon adsorption in the monolayer range are discussed. In general there are two possible contributions, the effect of the adsorbed layer itself and the effect due to a change in the substrate surface induced by the adsorbed layer. The latter effect occurs mainly in the case of chemical adsorption.The ellipsometric measurements on a number of clean semiconductor surfaces are treated and the results are compared with those obtained by other methods, e.g. electron energy loss spectroscopy and ultra-violet photon spectroscopy.     

Electron loss spectroscopy study of the growth by laser ablation of ultra-thin diamond-like films on Si(100)

Carbon films with thicknesses up to 10 monolayers (ML) have been grown on Si(100) substrates by means of laser ablation of graphite under ultra-high vacuum (UHV) conditions. The early stages of the growth have been characterized by Auger-electron (AES), electron-energy-loss (EELS) and ion-scattering (ISS) spectroscopies. EELS and AES can be used to qualitatively distinguish between the graphitic or diamond-like character of the films. The effect of submonolayer coverages on the surface electronic density of the silicon substrate has also been investigated. Carbon does not diffuse into silicon for room temperature depositions. Annealing at 950 °C causes graphitization and the formation of silicon carbide together with an intermixing of C and Si.     

Interface structures and rotational epitaxy of titanium on tungsten (110)

Interface structures of ultrathin Ti films grown on W(110) have been studied by low energy electron diffraction (LEED) and Auger electron spectroscopy (AES) in a wide range of annealing temperatures. The interface structures observed are interpreted to be due to site-coincidence growth (commensurate growth) and rotational epitaxy (incommensurate growth), respectively. The first monolayer of titanium is very strained with a large unit-cell expansion of 12.7% relative to that of Ti(0001). Deposition of additional Ti atoms destroys the strained structure, leading to rotational epitaxy: two Ti(0001) domains rotating mutually by 9.9 °. A thermally stable Ti bilayer exists at high annealing temperatures.     

Solid phase epitaxial growth of Si on Si---Sb surface phases for the formation of δ-doped layers and δiδi-superlattices

The SPE growth of Si on Si---Sb surface phases has been studied by LEED and AES techniques. The surface phases studied were the disordered Si(100)---Sb and the ordered one. Both surface phases have an Sb coverage of about one monolayer. Structures with single δ-doped layers and a δiδi-superlattice have been grown. The structural perfection of the grown Si films has been characterized on the basis of LEED data. The peculiarities of the annealing behaviour of Si films thinner than 10 nm have been detected.     

Formation of Co ultrathin films on Si(1 1 1): Growth mechanisms, electronic structure and transport

The AES, EELS, AFM and resistance measurement investigations have been performed to determine the growth mechanism, electronic structure and resistance-thickness dependence of Co layers on silicon at the thickness range from submonolayer up to several monolayer coverage. These layers were obtained under UHV high-rate deposition with using re-evaporation of Co from a Ta foil. The layer-by-layer growth of Co on Si(1 1 1) with some light segregation of Si has been found on the AES data. An enlarged and reduced concentration of valence electrons in the interface Si layer at the thickness ranges 0-1 Å and in the Co film at d = 1-2 Å has been observed. Resistance measurement of the Co film showed a fast decrease of the resistance down to some value limited by quantum-size effect in accordance with the formation of a two-dimensional Co phase at d = 1-2 Å.     

Cu adsorption on Pt(111) and its effects on Chemisorption: A comparison with electrochemistry

The growth modes and interaction of vapor-deposited Cu on a clean Pt(111) surface have been monitored by Auger electron spectroscopy (AES), low energy electron diffraction (LEED), and work function measurements. The LEED data indicate that below 475 K Cu grows in p(1 × 1) islands in the first monolayer with the interatomic Cu spacing the same as the Pt(111) substrate. The second monolayer of Cu grows in epitaxial, rotationally commensurate Cu(111) planes with the CuCu distance the same as bulk Cu. For substrate temperatures below ～ 475 K, the variation of work function and “cross-over beam voltage” with Cu coverage show characteristic features at one monolayer that are quite useful for calibration of θ_Cu. Above 525 K, Cu-Pt alloy formation was observed in AES and LEED data. Thermal desorption spectroscopy of H₂ and CO has demonstrated that simple site blocking of the Pt(111) surface by vapor-deposited Cu occurs linearly with chemisorption being essentially eliminated at θ_Cu = 1.0–1.15. Conclusions drawn from this work correlate very favorably with the well-known effects of under potentially deposited copper on the electrochemistry of the H₂2H⁺ couple at platinum electrodes.     

EELS characterization of TiN grown by the DC sputtering technique

Titanium nitride thin films were deposited on monocrystalline silicon (mc-Si) substrates by direct current reactive magnetron sputtering. Auger electron spectra (AES) of deposited films at different nitrogen partial pressures, show the typical N KL₂₃L₂₃ and Ti L₃M₂₃M₂₃ Auger transition overlapping. Also, changes in the Ti L₃M₂₃M₄₅ Auger transition peak are observed. X-ray diffraction and high resolution electron microscopy (HRTEM) of a golden color TiN/mc-Si sample, reveal a preferential polycrystalline columnar growth in the 〈111〉 orientation. This sample was also analyzed by electron energy-loss spectroscopy (EELS). The N/Ti elemental ratio is slightly different to the value determined by AES. Atomic distribution around the N atoms is in agreement with that expected from the N atom in the fcc unit cell of TiN. This distribution was obtained via an extended energy-loss fine structure (EXELFS) analysis from EELS spectra.