Spectroscopy techniques Auger

Surface analysis has made enormous contributions to the field of adhesion science. It enabled investigators to probe fundamental aspects of adhesion such as the composition of anodic oxides on metals, the surface composition of polymers that have been pretreated by etching, the nature of reactions occurring at the interface between a primer and a substrate or between a primer and an adhesive, and the orientation of molecules adsorbed onto substrates. Surface analysis has also enabled adhesion scientists to determine the mechanisms responsible for failure of adhesive bonds, especially after exposure to aggressive environments. The objective of this chapter is to review the principals of surface analysis techniques including attenuated total reflection (ATR) and reflection-absorption (RAIR) infrared spectroscopy. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and secondary ion mass spectrometry (SIMS) and to present examples of the application of each technique to important problems in adhesion science. 

Fein, A.P. J. Vac. Sci. Technol. A. in press)(3). Electronic structure measurements of occupied states are typically made with UPS, while unoccupied states are probed by IPS (49). EELS probes both filled and unfilled states simultaneously, and is therefore used in conjunction with either UPS or IPS to complete a band structure determination (44,49). A new electronic spectroscopy technique, Field Emission Scanning Auger Microscopy (50), utilizes STM-like technology to effect highly localized (c.a. 1 /im) Auger electron spectroscopy. The local electronic information afforded by STM is a valuable complement to these other techniques, and STM is the only one of these methods that may be applied to in situ investigations in condensed media. 

Spectroscopy produces spectra which arise as a result of interaction of electromagnetic radiation with matter. The type of interaction (electronic or nuclear transition, molecular vibration or electron loss) depends upon the wavelength of the radiation (Tab. 7.1). The most widely applied techniques are infrared (IR), Mossbauer, ultraviolet-visible (UV-Vis), and in recent years, various forms ofX-ray absorption fine structure (XAFS) spectroscopy which probe the local structure of the elements. Less widely used techniques are Raman spectroscopy. X-ray photoelectron spectroscopy (XPS), secondary ion imaging mass spectroscopy (SIMS), Auger electron spectroscopy (AES), electron spin resonance (ESR) and nuclear magnetic resonance (NMR) spectroscopy. 

Over the past 10 years a multitude of new techniques has been developed to permit characterization of catalyst surfaces on the atomic scale. Low-energy electron diffraction (LEED) can determine the atomic surface structure of the topmost layer of the clean catalyst or of the adsorbed intermediate (7). Auger electron spectroscopy (2) (AES) and other electron spectroscopy techniques (X-ray photoelectron, ultraviolet photoelectron, electron loss spectroscopies, etc.) can be used to determine the chemical composition of the surface with the sensitivity of 1% of a monolayer (approximately 1013 atoms/cm2). In addition to qualitative and quantitative chemical analysis of the surface layer, electron spectroscopy can also be utilized to determine the valency of surface atoms and the nature of the surface chemical bond. These are static techniques, but by using a suitable apparatus, which will be described later, one can monitor the atomic structure and composition during catalytic reactions at low pressures (< 10-4 Torr). As a result, we can determine reaction rates and product distributions in catalytic surface reactions as a function of surface structure and surface chemical composition. These relations permit the exploration of the mechanistic details of catalysis on the molecular level to optimize catalyst preparation and to build new catalyst systems by employing the knowledge gained. 

The corrosion deposits can be analyzed by X-ray photoelectron spectroscopy and Auger electron spectroscopy. Some characteristics of the techniques are ... 

The empirical approach adopted here integrates classical electrochemical methods with modem surface preparation and characterization techniques. As described in detail elsewhere, the actual experimental procedure involves surface analysis before and after a particular electrochemical process the latter may vary from simple inunersion of the electrode at a fixed potential to timed excursions between extreme oxidative and reductive potentials. Meticulous emphasis is placed on the synthesis of pre-selected surface alloys and the interrogation of such surfaces to monitor any electrochemistry-induced changes. The advantages in the use of electrons as surface probes such as in X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), high-resolution... 

Recently, new instrumental techniques have become available for determining surface structures on an atomic scale. These include X-ray fine structure (EXAFS), electron spectroscopies, ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), ion spectroscopies, secondary-ion... 

In the case of alloy electrocatalysts, the identification of the alloy constituent (at the topmost layers) during the electrocatalytic reaction is rather difficult. Therefore, the assumption of stability after the reaction makes the study rather simpler. In this case, the UHV conditions can be applied only in the ex situ variation, and then an idea of the process mechanism is also required. Not many techniques can be used for the identification of the alloy constituents. However, techniques under a high vacuum condition are applied x-ray photoelectron spectroscopy (XPS), Auger spectroscopy, low-energy ion scattering, and low-energy electron diffraction. 

A fourth process can also occur, as shown in Fig. 8.1 (d). Instead of emitting an X-ray photon, the energy released knocks an electron out of the M shell. This electron is called an Auger electron. This Auger process is the basis for a sensitive surface analysis technique. Auger electron spectroscopy and the related method of X-ray photoelectron spectroscopy, based on the measurement of the emitted electron shown in Fig. 8.1(b), are discussed in Chapter 14. 

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