Chemical analysis, with photoelectron spectroscopy

The chemical composition of the surface can be evaluated from the integrated intensities of the core-level emissions [31]. Unfortunately, the accuracy of quantitative analysis with photoelectron spectroscopy is generally limited to a few percent even when good standards are available [31]. Therefore, even from a large number of measured samples it was not possible to observe a... 

Jonsson et al. used synchrotron radiation to study the kinetic energy of photoelectrons from the S(2p) core level in PEDOTPSS films in electron spectroscopy for chemical analysis (ESCA). Photoelectrons from the S(2p) core level can be used as a quantitative measure of sulfur atoms in the aromatic thiophene ring of PEDOT and sulfur atoms in the sulfonic acid unit of PSS in the top layer of the film. By variation of the energy of the photons, the escape depth of photoelectrons from the polymer film can be tuned and a depth profile of the film can be obtained. Using this technique the authors demonstrated that pristine PEDOTPSS films have a PSS rich surface. With a photon energy of 270 eV, 95% of the signal stems from the outmost 15 A and a clear dominance of PSS is observed (see Table 9.4). When NMP and sorbitol are used as additives and the film is dried at room temperature, no PSS rich... 

X-ray photoelectron spectroscopy (XPS), which is synonymous with ESCA (Electron Spectroscopy for Chemical Analysis), is one of the most powerful surface science techniques as it allows not only for qualitative and quantitative analysis of surfaces (more precisely of the top 3-5 monolayers at a surface) but also provides additional information on the chemical environment of species via the observed core level electron shifts. The basic principle is shown schematically in Fig. 5.34. 

We shall concern ourselves here with the use of an X-ray probe as a surface analysis technique in X-ray photoelectron spectroscopy (XPS) also known as Electron Spectroscopy for Chemical Analysis (ESCA). High energy photons constitute the XPS probe, which are less damaging than an electron probe, therefore XPS is the favoured technique for the analysis of the surface chemistry of radiation sensitive materials. The X-ray probe has the disadvantage that, unlike an electron beam, it cannot be focussed to permit high spatial resolution imaging of the surface. 

XPS or ESCA (electron spectroscopy for chemical analysis) is a surface sensitive technique that only probes the outer atomic layers of a sample. It is very useful tool to study polymer surfaces [91]. An XPS spectrum is created by focusing a monochromatic beam of soft (low-energy) X-rays onto a surface. The X-rays cause electrons (photoelectrons) with characteristic energies to be ejected from an electronic core level. XPS, which may have a lateral resolution of ca. 1-10 pm, probes about the top 50 A of a surface. 

The work of Siegbahn s group who, in the 1950s, improved the energy resolution of electron spectrometers and combined it with X-ray sources. This led to a technique called electron spectroscopy for chemical analysis (ESCA), nowadays more commonly referred to as X-ray photoelectron spectroscopy (XPS) [6]. Siegbahn received the Nobel Prize for his work in 1981. Commercial instruments have been available since the early seventies. 

This technique is also known as electron spectroscopy for chemical analysis (ESCA). Although it is concerned with the detection of electrons, it is discussed here because the way in which the photoelectrons are produced is fundamental to the XRF process. As described above, an incident X-ray photon produces an excited ion by ejecting an inner shell electron. The excited... 

Although not capable of the micrometer-sized lateral resolutions available with the aforementioned techniques, the surface spectroscopy, electron spectroscopy for chemical analysis (ESCA), also deserves mention. The ESCA experiment involves the use of X-rays rather than electrons to eject core electrons (photoelectrons), and it has comparable surface specificity and sensitivity to that of Auger electron spectroscopy (AES) (25, 26, 29). The principal advantage of ESCA relative to AES is that small... 

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