Surface analysis technique

4 Surface Analysis Techniques Morphological Properties of Supported Clusters 

The microscopic structure of small clusters on surfaces is of primordial interest as it influences most of their physical and chemical properties. Acquiring 

Atomically Resolved STM Images of Clusters and Particles on Surfaces 

Counting Cluster Atoms by Using Rare Gas Decoration 

An indirect method to image small clusters on surfaces was obtained for size-selected Agj g clusters on a Pt(fff) surface where the cluster was decorated with rare gas atoms [197]. 

Surface analysis uses different techniques to probe the surface leading to a response, an analytical signal serving as a source of analytical information. The probe/ response combinations used in surface analysis include electrons, ions, photons, neutrals, heat, and electric field. Practically all combinations may form the basis of techniques used in surface analysis and so their list is rather long and should by no means be considered to be complete. This is also due to fact that very subde variations of a technique sometimes become known by their own name and acronym. Some of these acronyms are listed in the Appendix, Section 13.6. 

There are several ways to classify the surface analysis techniques. 

Photon Probe Techniques, divided further according to the fundamental process used  

The lUPAC Compendium of Analytical Nomenclature, Definitive Rules 1997 recommends the following scheme  

Handbook of Spectroscopy, Volume 1. Edited by Gunter Gauglitz and Tuan Vo-Dinh 

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Table 1. Overview of Common Surface Analysis Techniques...

Imaging of Surfaces—Analysis of Surface Morphology. Several important techniques can help answer the question what does the surface look like This question is often the first one to be posed ia the characterization of a new surface or iaterface. Physical imaging of the surface is necessary to distinguish the relevant features important for understanding the whole surface and is essential for accurate iaterpretation of data from other surface analysis techniques which might later be appHed to a more limited region of the surface or iaterface. 

The detection of impurities or surface layers (e.g., oxides) on thick specimens is a special situation. Although the X-ray production and absorption assumptions used for thin specimens apply, the X-ray spectra are complicated by the background and characteristic X rays generated in the thick specimen. Consequently, the absolute detection limits are not as good as those given above for thin specimens. However, the detection limits compare very favorably with other surface analysis techniques, and the results can be quantified easily. To date there has not been any systematic study of the detection limits for elements on surfaces however, representative studies have shown that detectable surface concentrations for carbon and... 

Although SIMS is one of the most powerful surface analysis techniques, its application is complicated by a variety of artifacts. 

In other articles in this section, a method of analysis is described called Secondary Ion Mass Spectrometry (SIMS), in which material is sputtered from a surface using an ion beam and the minor components that are ejected as positive or negative ions are analyzed by a mass spectrometer. Over the past few years, methods that post-ion-ize the major neutral components ejected from surfaces under ion-beam or laser bombardment have been introduced because of the improved quantitative aspects obtainable by analyzing the major ejected channel. These techniques include SALI, Sputter-Initiated Resonance Ionization Spectroscopy (SIRIS), and Sputtered Neutral Mass Spectrometry (SNMS) or electron-gas post-ionization. Post-ionization techniques for surface analysis have received widespread interest because of their increased sensitivity, compared to more traditional surface analysis techniques, such as X-Ray Photoelectron Spectroscopy (XPS) and Auger Electron Spectroscopy (AES), and their more reliable quantitation, compared to SIMS. 

Initial results prove the high potential of LA-based hyphenated techniques for depth profiling of coatings and multilayer samples. These techniques can be used as complementary methods to other surface-analysis techniques. Probably the most reasonable application of laser ablation for depth profiling would be the range from a few tens of nanometers to a few tens of microns, a range which is difficult to analyze by other techniques, e. g. SIMS, SNMS,TXRE, GD-OES-MS, etc. The lateral and depth resolution of LA can both be improved by use of femtosecond lasers. 

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. 

As indicated above, the penetration depth is on the order of a micrometer. That means that in ATR, absorption of infrared radiation mostly occurs within a distance 8 of the surface and ATR is not as surface sensitive as some other surface analysis techniques. However, ATR, like all forms of infrared spectroscopy, is very sensitive to functional groups and is a powerful technique for characterizing the surface regions of polymers. 

From the preceding discussion, it is evident that surface analysis techniques have contributed greatly to the understanding of adhesion related phenomena. Surface analysis has made it possible for adhesion scientists to determine the composition... 

The interface properties can usually be independently measured by a number of spectroscopic and surface analysis techniques such as secondary ion mass spectroscopy (SIMS), X-ray photoelectron spectroscopy (XPS), specular neutron reflection (SNR), forward recoil spectroscopy (FRES), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), infrared (IR) and several other methods. Theoretical and computer simulation methods can also be used to evaluate H t). Thus, we assume for each interface that we have the ability to measure H t) at different times and that the function is well defined in terms of microscopic properties. 

A number of techniques are available for determining the composition of a solid surface. Since the surface plays an important role in many processes, such as oxidation, discoloration, wear, and adhesion, these techniques have gained importance. The choice of a surface analysis technique depends upon such important considerations as sampling depth, surface information, analysis environment, and sample suitability. Different... 

Fig. 2. Schematic diagram of some surface analysis techniques. Abbreviations are explained in Table 1 and in the text...

There are still other surface analysis techniques including ellipsometry, surface enhanced Raman scattering, light scattering, nano-hardness measurements etc. which are used for specific investigations. It is, however, already evident from this discussion that many new and powerful techniques now are available which offer the capability of investigating various aspects of polymer surfaces on a molecular level. Some of those techniques are surface specific while others can be used for the analysis of buried interfaces, too. 

Application of Surface Analysis Techniques in the Study of Catalyst Systems... 

IR, etc. The chemical and physical changes within 3nm of the surface of the pellet or fluidized bead can be studied by surface analysis techniques such as AES, XPS, ISS, SIMS, RBS, etc. 

Laser microprobe MS (LMMS) can be used for direct analysis of normal-phase HPTLC plates [802,837]. Kubis et al. [802] used polyamide TLC plates polyamide does not interfere with compound identification by the mass spectrum, owing to its low-mass fragment-ions (m/z < 150). LMMS is essentially a surface analysis technique, in which the sample is ablated using a Nd-YAG laser. The UV irradiation desorbs and ionises a microvolume of the sample the positive and negative ions can be analysed by using a ToF mass spectrometer. The main characteristics of TLC-LMMS are indicated in Table 7.84 [838],... 

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. 

UHV techniques are usually classified in terms of the electron/photon method, as is shown in Table 2.3 which lists the common electron bombardment and emission techniques that have been employed in electrochemical studies. A detailed description of UHV surface analysis techniques is beyond the scope of this book there are many excellent reference texts that can be consulted for this purpose (see further reading list). It is sufficient to note that methods involving electron bombardment or emission are inherently surface-sensitive as a result of the low pathlength, or escape depth, of electrons in condensed media. In addition, Table 2.3 briefly describes the type of information each method provides. 

This is a surface analysis technique, used, for example, in examining causes of bonding failure. 

A surface analysis technique used in bonding failure analysis, for example. 

There is a wealth of information available on CO chemisorption over single-crystal and polycrystalline platinum surfaces under ultrahigh-vacuum conditions research efforts in this area have gained a significant momentum with the advent of various surface analysis techniques (e.g., 2-8). In contrast, CO chemisorption on supported platinum catalysts (e.g., 9, 10, 11) is less well understood, due primarily to the inapplicability of most surface-sensitive techniques and to the difficulties involved in characterizing supported metal surfaces. In particular, the effects of transport resistances on the rates of adsorption and desorption over supported catalysts have rarely been studied. 

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