AES and photoemission studies of Cu growth on Cr2O3

The initial growth (1–20 Å) of Cu on Cr₂O₃ at room temperature has been investigated by Auger Spectroscopy and UV photoemission spectroscopy by synchrotron radiation. Analysis of the Auger peak intensities suggests that copper is growing in a layer-by-layer mode probably with the simultaneous formation of the second and third layers.The photoemission spectra show that deposited copper grows steadily as a single copper species which does not interact strongly with the substrate.     

AES analysis of copper growth on MnO

The growth of Cu film on MnO substrate at room temperature has been investigated using Auger electron spectroscopy. Analysis of the Auger peak intensity as a function of Cu coverage and comparison of the experimental results with predictions of a layer-by-layer growth model, suggest that, at least in the first 16 Å of coverage, the growth of copper takes place in a layer-by-layer mode, simultaneously with the diffusion of some copper in the MnO substrate.     

Layer-by-layer growth of metal overlayers

We have used plots of the Auger amplitudes versus deposition time to investigate the growth mode of 3d-transition metals on noble metal (100) surfaces. The systems considered are Fe/Cu(100), Fe/Au(100), Co/Cu(100), and Cr/Ag(100). We find that: 1. The Auger plots consist of a succession of straight lines of constant length with sharp breaks in between, i.e. the growth mode is essentially layer-by-layer. 2. From the experimental data points a slight rounding off in the vicinity of the break points cannot be excluded, although a numerical analysis shows that the deviation from perfect layer-by-layer growth is less than 10% of a monolayer for all systems considered.     

Geometric structure and electronic states of copper films on a ruthenium (0001) surface

Auger electron spectroscopy (AES), combined with thermal desorption mass spectroscopy (TDS), work function (Δφ) measurements and energy-dependent angular resolved UV photoemission using synchrotron radiation were used to investigate the geometric and electronic properties of submonolayer and monolayer copper films grown by vapor deposition on a clean Ru(0001) substrate. A pronounced influence of the deposition temperature on the morphology of the Cu films was established in that lower temperatures favor an island growth mechanism (Stranski-Krastanov or Volmer-Weber type), whereas higher deposition temperatures lead to a more uniform spreading and a layer-by-layer growth (Frank-van der Merwe type). For Cu films grown under the latter conditions angular resolved photoemission reveals the existence of two-dimensional Cu bands even before the monolayer has reached completion; the experimentally determined band dispersions agree quite well with recent theoretical calculations.     

Leed measurements of Fe epitaxially grown on Cu(100)

Iron was epitaxially grown on a Cu(100) surface. Low energy electron diffraction (LEED) intensity versus energy curves were recorded for 1 and 10 layers of iron on Cu(100) at room temperature. A full dynamical analysis was performed using the renormalized forward scattering perturbation method. The surface Debye temperatures were determined to be 233 K for 1 ML Fe and 380 K for 10 layers of Fe. The value obtained for fcc iron was 550 K. A multiple relaxation approach was employed in analyzing the experimental data. The estimated interlayer spacings for the first and second layers were 1.78±0.02 Å (first) and 1.81±0.02 Å (second) for 1 ML Fe, and 1.81±0.02 Å (first) and 1.78±0.02 Å (second) for 10 layers of Fe on Cu(100). Auger electron spectroscopy was used to determine the thickness of the Fe films, and the LEED measurements indicate approximately a layer-by-layer growth until about 17 layers at room temperature. At higher temperatures there is evidence of iron diffusion or copper surface segregation.     

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.     

Leed,auger, and electron energy loss studies of Ni epitaxially grown on Cu(100)

Nickel was epitaxially deposited onto a clean, flat Cu(100) surface. Low energy electron diffraction I(E) curves were recorded for 0.6, 1.1, and 2.7 monolayer (ML) Ni coverage. Multilayer relaxation was considered in theoretical calculations, which were compared with experiment by means of the R|ΔE| factor. The estimated relaxations of the first and second interlayer spacings are estimated to be − 2% and + 1.5% for clean Cu(100), − 2% and − 1.5% for 1 ML Ni coverage, relative to the bulk Cu interlayer spacing of 1.81 Å, and −1% and 0% for 3 ML Ni coverage, relative to the bulk Ni spacing of 1.76 Å. Decreasing the surface Debye temperature of the Ni layer to 268 K from the bulk value of 440 K improves the agreement between theory and experiment. The optimum inner potential values are − 9 and − 10 eV for clean Cu(100) and Ni on Cu(100), respectively. Auger electron spectroscopy was used to determine the thickness of the Ni films, and LEED indicates layer-by-layer growth until about 4 layers, when the LEED spots begin to spread, indicating island formation. Electron energy loss spectra were obtained with primary electron energies of 150 and 300 eV. The 3p core ionization transition was clearly observed after 0.5 ML Ni coverage. Peaks at 3.8 and 7.5 eV for clean Cu are ascribed to interband transitions, and shift to higher energy with Ni coverage. Peaks at 10 and 16 eV for clean Cu (ascribed to an interband transition and a surface plasmon, respectively) disappear with Ni coverage. Bulk plasmon peaks at 19 and 27 eV remain unshifted with Ni coverage. The effect of 0.9 and 1.3 ML Ni coverage of Cu(100) on the chemisorption of Co and oxygen was also studied. The behavior of the surface towards oxygen chemisorption was similar to that of the pure Ni surface. For a large exposure of oxygen (50 L and more) the EEL and Auger spectra are very similar to those observed for NiO. In the case of CO, for submonolayer Ni coverage, the surface shows a more Cu-like behavior, while for larger Ni coverage (a monolayer and more) there is a great similarity with the behavior of the pure Ni(100) surface.     

Characterization of copper-exchanged Na-A,X and Y zeolites with X-ray photoelectron spectroscopy and transmission electron microscopy

Copper-exchanged sodium- A, X and Y zeolites have been characterized with X-ray photoelectron Spectroscopy (XPS), with supporting electron microscopy and X-ray diffraction measurements. Under reducing conditions (CO, H₂, 250–450° C), four distinct chemical states of copper have been identified. These are intrazeolite Cu(II), Cu(I) and 1 nm metal clusters, and externally segregated copper metal crystallites. We report spectroscopic data for both the Cu 2p_{$\text{3}\text{2}$} and Auger L₃M_4,5M_4,5 lines. Whereas Cu(II) and metallic copper crystallites have normal spectroscopic parameters, Cu(I) and 1 nm Cu clusters in the reduced zeolites lie in new areas of the two-dimensional chemical state plot.The reduction sequence of Cu(II), Cu(I), Cu clusters and Cu crystallites is different on the A zeolite compared with X and Y. One nm metal clusters are identified as an intermediate phase on the A with transmission electron microscopy (TEM) and XPS prior to external diffusion and crystallite formation. The ease of formation of the cluster intermediate in the A zeolite may be a consequence of the larger diffusion barrier imposed by the 0.42nm supercage aperture compared with the 0.74nm aperture in the X and Y zeolites.     

Evidence of epitaxial growth of bcc Co on Cr(100)

We report a LEED/Auger study of the growth of cobalt ultra-thin films on Cr(100) surfaces. We demonstrate that Co can be grown epitaxially at room temperature, probably in a metastable bcc phase on this chromium surface. A 1 × 1 LEED pattern is observed at least up to 20 cobalt monolayers. The Auger data are consistent with an abrupt interface and a layer-by-layer growth mode.     

Leed and Aes study of the Au/AuPb2 interface

The adsorption of lead on gold at room temperature in UHV conditions has been studied by LEED and AES. We review some of the data obtained on the Au(100), (111), and (110) faces, published elsewhere, and we give some new experimental results on the stepped Au(S) [n(100) × (111)] (with n = 3, 4, 5, and 6) faces. On all these faces, as lead is deposited on the gold substrate it first forms a monolayer of lead, then a compound AuPb₂. Using the LEED and Auger data we give a model of the epitaxy with a layer-by-layer growth mechanism. We propose a model which involves a transition alloy wich forms at the interface Au/AuPb₂. This model is in agreement with the LEED diagrams observed before the one corresponding to bulk AuPb₂. In the case of the epitaxy of lead on gold (100), we calculate the Auger peak-to-peak ] heights of the gold (72 eV) and lead (93 eV) transitions versus coverage. We obtain good agreement with the experimental data, assuming that the first and last layers of the alloy are lead monolayers and diffusion of lead in gold as well as gold in lead.     

AES studies of palladium films formed on copper and mica

Thin epitaxial films of palladium were grown on epitaxial copper films and cleaved mica in ultra high vacuum. The growth modes of these films were investigated by Auger electron spectroscopy (AES), low energy electron diffraction (LEED), transmission electron microscopy (TEM), and TEM replica techniques. Layer by layer growth of Pd on Cu and mica was observed and inelastic mean free paths of Auger electrons for energies of 60 eV (Cu MMM) and 329 eV (Pd MNN) were calculated. These values were 5.7 and 6.9 Å respectively. The thermal stability of monocrystalline and polycrystalline Pd/Cu bilayer films at 483 K was also investigated by AES and TEM. It was found that Pd agglomerates on the Cu at this temperature to form a Stranski-Krastanov growth morphology. The agglomeration is much more rapid on polycrystalline films, suggesting that high surface diffusivity paths (grain boundaries and possibly other defects) enhance the surface diffusion of Pd on Cu.     

Investigation of the chemical state of copper in Cu/SiO2 composite films by x-ray photoelectron spectroscopy

The concentration and chemical state of copper in the subsurface region of Cu/SiO₂ composite films obtained by simultaneous magnetron sputtering from two sources (Cu and SiO₂) are determined by x-ray photoelectron spectroscopy (XPS). It is established that copper in the as-grown film is primarily in the form of unoxidized atoms dispersed in a SiO₂ matrix. Annealing of the film results in practically no oxidation, but about 70% of the copper atoms condense into metallic clusters with sizes below 10 Å in the subsurface region and about 50 Å in the bulk of the film. The changes in the binding energy of core electrons, and especially in the energies of Auger electrons, are so large in this situation that photoelectron and Auger spectroscopy are efficient methods for monitoring the chemical state of this composite material.     

A study of H2S adsorption kinetics on the clean and oxygen covered (110) surface of copper

The very low pressure adsorption kinetics of H₂S on the clean and oxygen covered Cu(110) face have been examined by Auger Electron Spectroscopy (AES) and Mirror Electron Microscopy (MEM, used for continuous surface potential variations of the copper surface). The AES experimental curves on the clean copper face have been interpreted using a model of island growth by surface diffusion. The presence of an adsorbed oxygen layer on the copper surface changes notably the induction times observed on both AES and MEM measurements.     

ESCA studies of Cu,Cu2O and CuO

Cu 2p, Cu 3d and O 1s electron spectra and Cu L₃M_4,5M_4,5 Auger electron spectra from Cu, Cu₂O and CuO have been studied at 25°C and at 400°C. The height of the Cu 2p satellite peaks from copper oxides was lowered when the temperature was raised. The intensity of the satellites also decreased if the sample stayed in vacuum for prolonged periods.Two commercial cuprous oxides were different with respect to the behaviour of the satellite peaks. One produced very weak satellites, while the other produced strong ones as previously reported in the literature for cuprous oxide. The colour of the oxides was slightly different, indicating that the stoichiometry was not the same.The change in satellite intensity is accompanied by changes in oxygen spectra, Cu L₃M_4,5 M_4,5 Auger spectra and valence band spectra.It is useful to study Auger electrons in addition to the direct electron spectrum, since Auger signals can be more sensitive to surface conditions than direct electron spectra.     

Segregation effects in noble-metal film growth on Bi(0001): insights from Auger analysis

The growth of reactive adatom-substrate overlayers has been examined during the deposition of Ag and Cu on Bi(0001) using primarily Auger electron spectroscopy (AES) and low-energy electron diffraction (LEED). When viewed by the commonly used signal-versus-time plot, the Auger data exhibit a featureless behavior with a temperature dependence that is suggestive of cluster or compound formation. Surprisingly, when the same data are portrayed on a substrate-versus-adatom plot of the signals, the results are quite unlike those previously reported in the literature, in that the curvature of the data is the opposite of that typically found as the adatom signal increases. Heavy adatom deposition is needed to totally obscure the substrate signal. In the absence of factors that are known to affect the Auger yield in such overlayer systems, these data are found to be consistent with a growth process in which a layer of Bi substrate atoms is continuously segregated at the vacuum-solid interface. This interpretation is consistent with predictions from surface free-energy arguments, in that the Bi has a much lower energy than Ag or Cu and, thus, has a strong tendency to stay on top of the growing film.     

铜导线短路熔痕的XPS研究

利用氩离子溅射对熔痕样品进行了深度刻蚀,同时利用Cu的俄歇谱线和计算的俄歇参数值,对不同环境形成的铜导线短路痕迹的物相及元素分布规律进行了分析。根据刻蚀时间可将一次短路熔痕表面膜层分为三部分,即C含量迅速减少的近表面层;O含量变化不大,C含量逐渐消失且有Cu₂O相的中间层;无Cu₂O相,O含量显著减少的过渡层。而将二次短路熔痕表面膜层分为两部分：C含量迅速减少的近表面层;无Cu₂O相,C和O量逐渐减少层。由此可见,一次短路熔痕的表面膜层与基体分界明显,有显著的过渡层,而二次短路熔痕的表面膜层与基体分界不明显,无过渡层。综上所述,可以根据两种短路熔痕是否含有Cu₂O相以及定量分析结果来区分两种熔痕,为判断火灾原因提供新的技术依据。     

ESCA studies of some copper and silver selenides

Photoelectron and Auger spectra have been obtained for the copper and silver selenides CuSe, Cu ₂Se, Ag ₂Se, and AgCuSe as well as from CuS, Ag ₂O, Ag ₂S, Cu, and Ag. Binding-energy values, chemical shifts, and peak-shapes are reported for the Cu 3 d, Ag 4 d and Se 3 p electrons. Absence of multiplet splitting and shake-up structure is discussed in relation to the magnetic properties. It is shown that chemical shifts are much better revealed in the Auger spectra (Cu L₃M_4,5M_{4, 5} and Ag M₅N_{4, 5}N_{4, 5}) than in the direct photoelectron ones. In addition the use of the Auger parameter to characterize the series under study is emphasized. Finally the valence-band spectra have been examined and the electronic structures are interpreted.     

The interaction of hydrogen and carbon monoxide with oxygen on Cu(110)-Fe surfaces

The interaction of hydrogen and carbon monoxide with oxygen adsorbed on Cu(110)-Fe surfaces has been studied with ellipsometry, Auger electron spectroscopy and low energy electron diffraction. With carbon monoxide copper can be reduced completely and Fe_0.95O partially. With a model which is only an extension of the scheme for the reduction of pure Cu(110) by CO, the reduction of Cu(110)-Fe can be simulated. The lateral orientation of Fe_0.95O with respect to the copper matrix changes during repetitive oxidation-reduction cycles. At 725 K oxygen deficient iron oxide segregates to the surface. With hydrogen all oxygen can be removed.     

Chemisorption of Si on Al(111) surfaces: A local-chemical-bond analysis from Auger transition density of states

Auger and electron loss spectroscopies have been used to study the local chemical bond between Si and Al, in the first stages of growth of Si deposited at room temperature on Al(111) surfaces. Si follows a layer-by-layer mechanism up to 2 monolayers with the formation of an Al(111)-3 × 3-Si structure at about 0.44 monolayers. A detailed analysis of the L_2,3VV Auger spectra for this structure allows to interpret the Si and Al Auger transition density of states (TDOS) in terms of the actual p-like partial DOS centered on the Si and Al sites. The experimental results indicate a strong SiAl interaction with the formation of a p-type local covalent bond between the Si and Al surface atoms.     

Auger and other characteristic energies in secondary electron spectra from Al surfaces

The energy spectra of secondary electrons back-scattered from clean, oxygen covered, and Cu covered Al surfaces have been determined. The data support the previous suggestion that Auger electrons can experience both characteristic energy loss and absorption phenomena. From the experimental results it was not possible to determine whether densities of states of electrons in the valence band affected the Al L_2,3 VV Auger spectrum. This portion of the spectrum was greatly changed by oxygen absorption on the Al surface, but little affected by less than a monolayer of Cu. Conversely, characteristic loss spectra were less sensitive to oxygen on the surface, but were highly sensitive to the presence of copper at even less than monolayer coverage. A correlation between characteristic loss and “true” secondary spectra from clean surfaces was established and possible reasons for the correlation are discussed.