Applications of Auger and photoelectron spectroscopy
Auger and photoelectron spectroscopy principles, instrumentation, and applications
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Auger and photoelectron spectroscopy principles, instrumentation, and applications
X-ray photoelectron spectroscopy (XPS) is described in its application as a probe for studying defects such as sodium in SiO2 films. A general description is given of key experimental methods in XPS. Techniques are described for applying and monitoring a fixed bias at the surface of the oxide during the XPS measurement. These methods are shown to be capable of detecting extremely small Na and Cu concentrations in undoped samples (less than 10 to the 11th power per cu cm). In deliberately Na-doped samples, five spectral peaks are distinctly observed and related to different defect states at the vacuum/SiO2 and SiO2/Si interfaces. By applying a bias-temperature stress during the XPS measurements, these peaks change in relative intensity and can be related to the motion of the Na(+) ions between different states occurring at the two interfaces. An attempt is made to correlate the observations with previously reported models.
The effect of Sr and Bi on the oxidation of the Si(100) surface has been studied by Auger electron spectroscopy, low electron diffraction, and X-ray photoelectron spectroscopy. A dramatic enhancement, by a factor of 10, of the Si oxidation has been observed for Si(100) with a Sr overlayer. The SR-enhanced Si oxidation has been studied as a function of O2 exposure and Sr coverage. In contrast to the oxidation promotion of Sr on Si, it has been also observed that a Bi overlayer on Si(100) reduced Si oxidation significantly. Sr adsorption on the Si(100) with a Bi overlayer enhances Si oxidation only at Sr coverage of greater than 0.3 ML.
Detailed sequential study by photoelectron spectroscopy of the change in valence states of iron in Fe2O3, Fe3O4, FeO, and Fe foil samples, showing that chemical reduction does take place on the sample surface when argon ion bombardment occurs. These spectra give evidence that, after prolonged ion bombardment, the surface of all four samples consisted predominantly of iron in the metallic state. Argon ion sputtering of 15 silicate and oxide samples under similar experimental conditions produced surface darkening only in samples containing iron. Monitoring of the photoelectron peak of carbon during the experiment indicates that ion-bombardment darkening is not due to the buildup of hydrocarbon surface contaminants in the oil-free high-vacuum system used by the authors. On the basis of these studies, it is concluded that solar-wind bombardment should be included as one of the possible mechanisms for producing darkening of the lunar surface.
Polyatomic molecule photoelectron spectroscopy, emphasizing spectra interpretation by quantum mechanical procedures
Threshold photoelectron spectra of Ar and N2 are studied by a technique called threshold photoelectron spectroscopy by electron attachment, which involves the attachment of the threshold electron to SF6 followed by the detection of SF6(-). Studies on Ar provide a measure of the rejection ratio for nonthreshold electrons of this technique. A rotational propensity rule is given which states that an autoionizing N2 state prefers to decay to N2(+) states with a minimum change in rotational angular momentum.
Auger and photoelectron spectroscopy for chemical analysis, noting effects of sample thickness, sample potential, surface contamination and X ray incident angle
Three studies are described characterizing the possible contributions of surface science to tribology. These include surface contamination formed by the interaction of a surface with the environment, contaminants obtained with diffusion of compounds, and surface chemical changes resulting from selective thermal evaporation. Surface analytical tools such as Auger electron spectroscopy (AES) and x ray photoelectron spectroscopy (XPS) incorporated directly into adhesion and friction systems are primarily used to define the nature of tribological surfaces before and after tribological experimentation and to characterize the mechanism of solid-to-solid interaction. Emphasis is on fundamental studies involving the role of surfaces in controlling the adhesion and friction properties of materials emerging as a result of the surface analyses. The materials which were studied include metals and ceramics such as elemental metals, amorphous alloys (metallic glasses), and silicon-based ceramics.
Feasibibility study of Auger and photoelectron spectroscopy as analytical tool
X-ray photoelectron spectroscopy (XPS), Rutherford Back Scattering (RBS) studies of each of sample received were completed. Since low angle X-ray could not be performed because of instrumentation problems, Auger spectrometry was employed instead. The results of these measurements for each of the samples is discussed in turn.
The dependence of the nitrogen distribution in thermally nitrided SiO2 films on the nitridation time and temperature has been studied by means of X-ray photoelectron spectroscopy (XPS). The photoelectron peak intensities were measured by fitting Voigt profiles to the XPS spectra and were used to calculate the film composition as a function of film depth, applying an analytical method described in detail. The times of appearance of the maxima in interfacial nitrogen concentration are shown for 800, 1000, and 1150 C, and the data are related to a kinetic model of Vasquez and Madhukar (1985), which considers the effect of interfacial strain on the nitridation kinetics. In addition, the intensity of a fluorine marker (from the HF used in the etching step) was found to correlate with the nitrogen concentration. It is postulated that the F bonds preferentially to defects. This hypothesis and the measured F intensities are consistent with the proposed strain-dependent energy of defect formation.
The technique of X-ray photoelectron spectroscopy and the fundamental electronic interactions constituting the basis of the method will be discussed. The method provides information about chemical states ("oxidation states") of atoms in molecules. In addition, quantitative elemental analysis can be performed using the same method. On the basis of this information identification of chemical species is possible. Examples of applications are discussed with particular references to the study of smog particulate matter.
Discussion of the problem of measuring branching ratios or transition probabilities using the technique of photoelectron spectroscopy in terms of the angular distribution of the ejected photoelectrons. Equations are developed that can be used in conjunction with any type of electron-energy analyzer to correct for any discrimination in the analyzer caused by electrons of varying angular distribution. Results are presented for the branching ratios of the A super 2 pi sub u and B super 2 sigma sub u (+) states of CO2(+) produced by 584 A and obtained by a variety of electron-energy analyzers.
A new technique for measuring high-resolution threshold photoelectron spectra of atoms, molecules, and radicals is described. It involves photoionization of a gaseous species, attachment of the threshold, or nearly zero electron to some trapping molecule (here SF6 or CFCl3), and mass detection of the attachment product (SF6/-/ or Cl/-/ respectively). This technique of threshold photoelectron spectroscopy by electron attachment was used to measure the spectra of argon and xenon at 11 meV (FWHM) resolution, and was also applied to CFCl3.
The effect of the X-ray flux in X-ray photoelectron spectroscopy (STAT) on the constitution of the polytetrafluoroethylene (PTFE) surface has been examined. The radiation dose rate for our specimen was about 10 to the 7th rad/s. The structure, magnitude and binding energy of the C(1s) and F(1s) features of the XPS spectrum and the mass spectrum of gaseous species evolved during irradiation are observed. The strong time dependence of these signals over a period of several hours indicated that the surface constitution of PTFE is greatly affected by this level of radiation dose. The results are consistent with the development of a heavily cross-linked or branched structure in the PTFE surface region and the evolution of short chain fragments into the gas phase.
X-ray photoelectron spectroscopy has been used to study the composition of 100-A thermally grown SiO2 films that have been thermally nitrided in ammonia. The SiO(x)N(y)/Si interface was studied both by chemical depth profiling of the oxynitride and by removal of the Si substrate with XeF2. It is found that N is distributed throughout the film, but with the concentration higher at the surface and in a region centered 25 A from the film/substrate interface. The interface region itself is found to be oxygen-rich relative to the rest of the film. Possible models which can explain these results are discussed.
X-ray photoelectron spectroscopy is used to study the effects of heat treatment on the Pd/6H-SiC Schottky diode structure. After heating the structure at 425 C for 140 h, a very thin surface layer of PdO mixed with SiO(x) formed on the palladium surface of the Schottky structure. Heat treatment promoted interfacial diffusion and reaction which significantly broadened the interfacial region. In the interfacial region, the palladium concentration decreases with depth, and the interfacial products are Pd(x)Si (x = 1,2,3,4). In the high Pd concentration regions, Pd4Si is the major silicide component while gr and Pd2Si are major components in the low Pd concentration region. At the center of the interface, where the total palladium concentration equals that of silicon, the concentrations of palladium associated with various palladium silicides (Pd(x)Si, x= 1,2,3,4) are approximately equal. The surface passivation layer composed of PdO and SiO, may significantly affect the electronic and catalytic properties of the surface of the Schottky diode which plays a major role in gas detection. The electronic properties of the Schottky structure may be dominated by a (Pd+Pd(x)Si)/SiC interface. In order to stabilize the properties of the Schottky structure the surface and interface diffusion and reactions must be controlled.
Monochromatized angularly resolved X-ray photoelectron spectroscopy (ARXPS) was used to study PTFE (Teflon) that had been exposed to an earth orbital environment for approximately six years. The primary interest of the research is on a very reactive component of this environment (atomic oxygen) which, because of the typical orbital velocities of a spacecraft, impinge on exposed surfaces with 5 eV energy. This presentation deals with the method of analysis, the findings as they pertain to a rather complex carbon, oxygen, and fluorine XPS peak analysis, and the character of the valence bands. An improved bias referencing method, based on ARXPS, is also demonstrated for evaluating specimen charging effects. It was found that the polymer molecule tends to resist the atomic oxygen attack by reorienting itself, so that the most electronegative CF3 groups are facing the incoming hyperthermal oxygen atoms. The implications of these findings to ground-based laboratory studies are discussed.