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Surface Analysis
Alfred G. Hopkins 1

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This limits the n u m b e r of analysis points that can be obtained. All of the above limitations result in most studies being done on stable films on metals and making these techniques of lesser utility on unstable or rapidly changing systems.

BECAUSE CORROSIONis fundamentally a surface phenomenon, those interested in the fundamental processes of corrosion have always been among the first to explore the utility of surface analysis techniques. These techniques have had, and will continue to have, great success in illuminating m a n y facets of corrosion phenomena. For those seeking a more detailed treatment of the application of surface analysis techniques to the study of corrosion than can be given here, there are a n u m b e r of S y m p o s i u m Proceedings from the Electrochemical Society and from ASTM that are of great utility [1-6]. For those interested in more depth on the subject of surface analysis in general or on particular surface techniques, the following are some useful references [7-13]. Systems that are particularly amenable to surface analysis include inhibitor films and protective coatings, stable oxide films, and corroded surfaces.

GENERAL PRINCIPLES
These techniques generally require the sample to be placed in an ultrahigh vacuum (on the order of 10-7 P a / 1 0 - 9 torr) to prevent contamination from residual gases in the analysis chamber. A rule of t h u m b is that up to an atomic layer per second can be formed at pressures of 10-4 Pa (10-6 torr) if each collision of a gas molecule results in its sticking to the surface. Fortunately, the sticking coefficients are often m u c h less than unity, especially for oxidized samples such as often are of interest in corrosion studies. Some samples are especially prone to reacting with residual gases; this is often accelerated by electron beam-induced degradation at the sample surface with techniques such as Auger. In these cases, it m a y be necessary to bake the analysis system to reach vacuums in the low 10-8 Pa range or better. With some techniques (such as Secondary Ion Mass Spectroscopy), the v a c u u m requirements can be relaxed since the surface that is actually being analyzed will only be exposed to the vacuum for a very short period of time. Near surface techniques, in contrast to true surface techniques, do not require an ultrahigh vacuum. Secondary Electron Microscopy-Energy Dispersive X-ray Spectroscopy (SEMEDS) is an example of a particularly useful near surface technique that will be discussed in a later section. Micro surface electrochemical techniques, such as the Scanning Kelvin probe, overcome these limitations and do give detailed electrochemical (rather than elemental) information about the system in question. In classic surface analysis techniques, the surface is illum i n a t e d (interrogated) with high-energy electrons, photons, or ions. Depending on the illuminating species, any or all of these types of species will be generated from the ensuing collision. Elemental identification is then made based on characteristic energies or masses of the ejected species. One c o m m o n way of characterizing surface analysis techniques is by tabulating the incoming and outgoing particles. Table 1 shows such a table, which was adapted from previously published ones [8-10]; this paper will concentrate on the most frequently used techniques. Because surface analysis 76

LIMITATIONS
There are, however, a n u m b e r of limitations that have prevented these techniques from being even more widely used. The first is that corrosion is inherently a dynamic process, while these techniques are essentially static in nature. They can only give a snapshot in time of the chemical state of the system. These techniques are obviously of m o r e use in those systems that change slowly in time versus those that change rapidly. The second limitation is that most of these techniques require that the sample be removed from the corrosive envir o n m e n t and placed into a high vacuum environment before analysis can be performed. This is a major problem for those systems that can change structure u p o n drying or loss of absorbed water. The third major limitation is that the analysis process itself can change the composition of the surfaces to be analyzed. The two most c o m m o n types of this problem are analysis beam-induced damage and inhomogeneities caused by the sputtering process, which is used often to probe past the topmost surface of the sample. The final major limitation is cost/availability. Some of the techniques are not widely available, and even those that are easily available (XPS and Auger) are still quite expensive.

IDistinguished Member, Technical Staff, Texas Instruments Inc., Attleboro, MA 02703-0964.

Copyright* 2005 by ASTM International

www.astm.org

CHAPTER 4 - - S U R F A C E A N A L Y S I S 7 7

TABLE 1--Comparison of surface analysis techniques.

Category Technique Auger XPS-ESCA Dynamic Sims Static Sims SNMS SALI RBS ISS Incident Particle Electron X-Ray Ions Ions Ions Ions Ions Ions Analyzed Particle Auger Electron Photo-Electron Sec Ions Sec Ions Neutrals Neutrals Input Ions Input Ions Measured Quantity Energy Energy Mass Mass Mass Mass Energy EnergyAnalysisDepth in Monolayers 2-10 2-10 10-20 1-2 5-10 1-2 many 1 Sample Damage No-Mod No-Min Mod-Ext Mid-Mod Min-Ext Min-Ext Min-Mod No Sensitivity Standardless (AtomicFraction) Quantification 10 -3 fair 10-3 fair 10-7 poor 10-8 poor 10-7 fair 10-7 fair 10-3 good 10-3 good

NOTES---NO: NONE; MOD: MODERATE; MED: MEDIUM, EXT: EXTENSIVE.

is an extremely specialized field, it has its own nomenclature; the reader is referred to ASTM E 673, Terminology Relating to Surface Analysis. Surface analysis is mainly used in two separate modes. One is in surface science where the goal is to fundamentally u n d e r s t a n d the root causes and mechanisms that are occurring in a system. Usually a model system is picked to eliminate as m a n y confounding variables as possible to get a system about which firm conclusions can be drawn. Often, m a n y different techniques wilt he used o n the same problem i n order to illuminate as m a n y facets of the problem as possible. The other mode is failure analysis. The goal here is to determine which of the failure modes (previously discovered by surface science) is the most important one for a particular failure. The samples are real, and hence, nonideal. This analysis mode is often used to identify the elements present, their distribution pattern and their oxidation state. The first and second most c o m m o n of the true surface analysis techniques are Auger Electron Spectroscopy (AES) and X-ray Photoelectron Spectroscopy. They are electron spectroscopies that quantify the energy of electrons that are emitted by the surface during analysis. A good reference for those seeking more detail is "Uses of Auger Electron and Photoelectron Spectroscopes in Corrosion Science" by McIntyre and Chan in Practical Surface Analysis [12].

AUGER ELECTRON SPECTROSCOPY (AES)

AES is the most commonly used surface technique on metal samples because of the following advantages: 9 High-surface sensitivity. 9 Acceptable detectability for m a n y corrosion problems. 9 Simultaneous detection of all elements (except hydrogen and helium). 9 Very good small area analysis (mapping). 9 Ability to probe deeper into the surface by sputter profiling. 9 Analysis time not excessively long. 9 Readily available instrumentation. With AES, the sample is subjected to a high-energy (typically 2-20 KeV) electron beam that can cause ejection of a core electron from an atom to form an atomic inner shell vacancy. An outer-level electron will then fill the inner-level vacancy, which will induce an excited state. One of the ways that the atom can then relax is by emitting another electron to form a doubly ionized species. This electron is the Auger electron (named for Pierre Auger, who recognized the effect

in a Wilson Cloud Chamber and first described it in 1923) [14]. Because the emission of a n Auger electron is, in reality, a three-electron process, Auger transitions are n a m e d for the energy levels of the three-electron orbitals involved, such as KLL. The Auger process releases electrons of characteristic energy for each element, which are d e t e r m i n e d by the differences in energy of the orbitals involved. In addition to the Auger electrons, there are also m u c h more plentiful secondary electrons with a broad energy distribution that overlay the characteristic peaks. To highlight the characteristic peaks, differentiation is performed on a plot of the n u m b e r of electrons emitted by the sample versus the energy of those electrons. This results in a spectrum that ignores the more plentiful b a c k g r o u n d (secondary) electrons and emphasizes the characteristic electrons that are used to identify the elements present. In some cases, the exact peak shape a n d energy can be used to identify the oxidation state of the elements present. To more clearly discern the peaks, the spectra are derivatized; such a spect r u m is shown in Fig. 1. One of the attractions of Auger analysis is that it is quite surface-sensitive since an Auger spectrum typically represents information about the composition of the top (0.5-2 nm) of the surface depending on the sample analyzed and the analysis conditions. Although Auger electrons can be generated at depths of several micrometers into the sample, in order to be detected, the Auger electrons must be able to escape to the surface without undergoing an inelastic collision. The presence of overlaying material exponentially decreases the probability of the electron reaching the detector unscathed. The exponential constant is the inelastic mean-free path of the electron, which depends on the kinetic energy of the Auger electron and the material it must

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78

CORROSION TESTS AND STANDARDS MANUAL are shown in Fig. 2. Variations in signal intensity caused by geometric effects can often be eliminated b~" ratioing the intensity of the peak of interest to that of adjoining background areas. Elemental m a p p i n g is also an important tool in techniques such as SIMS, SEM-EDS, Scanning Kelvin Probe and others. As in most surface analysis techniques, qualitative identification of the elements present is the easiest type of analysis. Most elements have more t h a n one Auger peak due to having either multiple transitions or fine structure within a transition. It is fairly easy to identify from an Auger spect r u m what elements are present on the surface of the sample based on the following: peak position, peak intensity ratios for a particular element, and peak shape. Compilations of elemental spectra and charts of atomic n u m b e r versus electron energy are available to help assign peaks. Modern data processing (background subtraction, peak fitting to standard spectra) has m a d e it possible to correctly resolve m a n y peak identification problems caused by peak overlap. The analyst should be familiar with ASTM E 827, Standard Practice for Identifying Elements In Auger Electron Spectroscopy. There have been some variations in peak electron energy between different systems and handbooks, but this should be minimized in the future as a result of standardization efforts of ASTM. Both peak energy and peak shape can vary depending u p o n the chemical state of the element. This is particularly true for the low-energy transitions of valence electrons. It can also be seen in core-level transitions in those cases where the electrons experience strong energy losses in escaping from metallic surfaces b u t not from the oxide; for

traverse in order to reach the detector. Empirical graphs of the relationship between the electron kinetic energy and its mean-free path are often of use in understanding detectbility issues. The effective depth of analysis varies from element to element, even varying between lines of a particular element. This results in high-energy Auger electrons being detectable from deeper in the surface than low-energy ones. For example, a thin, adsorbed carbon (organic) film will preferentially mask the low-energy (68 eV) peak of a l u m i n u m as c o m p a r e d to the high energy one (1396 eV). These same types of considerations are applicable to all related electron spectroscopies such as XPS. Auger spectroscopy also offers acceptable detectibility for m a n y situations encountered in corrosion science. This can be as low as 0 . 0 1 % , although this is seldom realized in c o m m o n practice since low detectibility conflicts with other desirable qualities such as resolution, analysis time, and the need to minimize b e a m current to minimize b e a m damage. Almost all Auger spectrometers have a scannable incident electron b e a m such as is used in a Scanning Electron Microscope (SEM). Such an instrument can also be called a Scanning Auger Microscope (SAM). This can provide spatial resolution as low as 15 nm. The ability to scan allows elemental concentration maps of the surface to be generated. This qualitative analysis of small areas is AES's greatest strong point. Its ability to determine element identity and distribution via mapping provides insights into m a n y corrosion problems. In particular, the breakdown of passivity and the initiation of pitting corrosion are often associated with the presence of heterogeneous elements, which include both internal inclusions and corrosive species. Auger maps

FIG. 2mAuger elemental distribution maps.

CHAPTER 4
instance; aluminum, magnesium, and silicon. A more detailed description can be found in ASTM E 984, Guide for Identifying Chemical Effects and Matrix Effects in Auger Electron Spectroscopy. Auger spectrometers are normally equipped with ionb e a m sputter guns that can slowly remove the surface while the sample is being analyzed in the vacuum chamber. This results in a depth profile that plots the composition of the freshly generated surface as it varies with depth into the surface. The following three basic issues must be faced when sputter profiling is employed: difficulties in determining the sputter rate, variations in depth resolution, and changes in the sample that are induced by the ion beam. Sputter rates vary greatly depending on such factors as the identity of the ions (argon is most typical), the accelerating voltage, the angle of incidence, the chemical nature of the sample, and sample surface structure. Although published sputtering yields can be helpful, they cannot replace running known thickness standards on an individual instrument. Two standards that are easiest to accurately fabricate, and therefore are the most common, are tantalum oxide on tantalum and silicon oxide on silicon. Further complications are added by the dependence of sputter yield on depth and on surface roughness. Depth resolution can be considered to be equal to the observed broadening of an originally atomically sharp interface. It is not constant; it worsens as one sputters into the material. Inert gas ion sputtering is used in the great majority of surface analysis techniques, either as a method of seeing deeper into the sample (Auger, XPS) or as a way of generating particles to be analyzed (SIMS). A discussion of some of the effects of the sputtering process is given in the SIMS section of this chapter. An important publication on the subject is ASTM E 1127, Guide for Depth Profiling in Auger Electron Spectroscopy. A review of sputtering is given in "Depth Profiling in Corrosion Research" in Ref 15. F o r Auger spectroscopy, a simplistic m e t h o d of generating a sputter profile by plotting net p e a k heights works well if there are no p r o b l e m s such as: p e a k overlap, peak shape change, a n d p e a k shift. M o d e r n d a t a m a n i p u l a t i o n techniques such as factor analysis minimize the effects of these problems. An Auger sputter profile is shown in Fig. 3. Absolute quantification of surface composition by electronenergy spectral techniques such as Auger and ESCA is a very difficult goal. Current efforts are concentrated in abstracting

SURFACE A N A L Y S I S

79

quantifiable peaks from the spectra and in minimizing interi n s t r u m e n t a n d i n t e r - l a b o r a t o r y variations. ASTM Committee E-41 on L a b o r a t o r y Apparatus has a n u m b e r of s u b c o m m i t t e e s dealing with these issues for a n u m b e r of surface analysis techniques including Auger, ESCA, and SIMS. A relevant p u b l i c a t i o n is ASTM E 995, Guide to Backg r o u n d S u b t r a c t i o n Techniques in Auger Electron Spectroscopy. Auger analysis is subject to a n u m b e r of possible artifacts due to effects such as sample charging, electron b e a m desorption, electron b e a m decomposition, and variations i n d u c e d by sputter profiling. These are treated in ASTM E 983, S t a n d a r d Guide for Minimizing Unwanted Electron B e a m Effects in Auger Electron Spectroscopy. To prevent the analyst from adding c o n t a m i n a t i o n to the sample, he should be a w a r e of ASTM E 1078, Guide for S p e c i m e n Handling in Auger Electron Spectroscopy, XRay Photoelectron Spectroscopy, and S e c o n d a r y Ion Mass Spectrometry.

X-RAY PHOTOELECTRON SPECTROSCOPY

(XPS)

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Einstein received the Nobel Prize for his explanation of the photoelectric effect in which atoms can be ionized by an incoming p h o t o n [16]. Siegbahn's [17] realization that the energy of the ejected photoelectron could be used to determine the chemical state of an a t o m caused him to coin the name ESCA (Electron Spectroscopy for Chemical Analysis). Because X-ray photons are necessary to generate appropriate electrons, the technique is also called X-ray Photoelectron Spectroscopy (XPS). XPS shares the Auger characteristics of good surface sensitivity since this is driven by the same need for the electrons to be able to reach the detector unscathed. It is possible to vary the depth of analysis in both techniques by varying the tilt angle with regard to the detector. This technique is used more extensively in XPS where it is often called angle resolved depth profiling. XPS also has the very i m p o r t a n t advantage of being able to obtain chemical state information on most atoms. It becomes easy to observe the effect of differing chemical environments in both the photoelectron peaks and in the Auger peaks, which are also generated by XPS's X-ray excitation. Often, the chemical shifts in the Auger peaks of an XPS spectrum are larger than the shifts in the photoelectron peaks. Another aid to assigning the proper oxidation state to a peak is the presence of satellite shake-up lines due to a simultaneous promotion of a valence electron to a higher orbital as the photoelectron is being ejected. Proper interpretation of the implications of peak shifts requires the knowledge of sample charging on the spectra. A useful reference is ASTM E 1523, Guide to Charge Control and Charge Referencing Techniques in X-Ray Photoelectron Spectroscopy. Another advantage of XPS is that peak identification is more easily done than in Auger because of the narrow line width, as well as the presence of both Auger peaks and photoelectron peaks in the spectra as is shown in Fig. 4. XPS is also preferable in that it is able to analyze nonconducting samples and has a lesser tendency towards sample degradation than other techniques. XPS is not as preferable

80

C O R R O S I O N TESTS A N D S T A N D A R D S M A N U A L
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FIG. 4--Ultraviolet photon spectroscopy: uses of narrow scans for corrosion problem solving.

because it does not have Auger's very small spot size since it is m u c h more difficult to focus X-ray beams than electron beams. Therefore, it is necessary to mask or abstract only a portion of the available analysis area which negatively impacts the signal to noise ratio. Relevant information is found in ASTM E 1217, Practice for Determination of Specimen Area Contributing to the Detected Signal in X-Ray Photoelectron Spectroscopy and Auger Electron Spectroscopy. However, 10-30 gm size analysis is possible on a routine basis. The longer time necessary for an XPS spectrum often results in the analyst settling for a lower signal-to-noise ratio and, hence, poorer detectibility than with Auger.

SECONDARY ION MASS SPECTROSCOPY (SIMS)

Secondary Ion Mass Spectroscopy (SIMS) is the third of the three most c o m m o n surface analysis techniques. A good reference to SIMS and other ion spectroscopies is Czanderna's and Hercules' "Ion Spectroscopies for Surface Analysis" in Ref 11. In SIMS, the sample is irradiated with a primary ion beam (normally argon), the impact of which sputters away the surface atoms, some as neutrals and others as ions. Those atoms that become ionized are then detected in a mass spectrometer where their masses are measured. The most c o m m o n variant is Dynamic SIMS in which a high-energy ion beam is used that removes layers of the surface. The beam is so energetic that little chemical information is retained since the vast majority of any molecular species is fragmented. Although destroying the surface obviously prevents its re-examination, it is not a total disadvantage since it allows depth profiling to occur. Some of the advantages of SIMS are that it has a very low detection limit (PPM to PPT) and it can detect all elements. These advantages make it able to address many problems that neither AES nor XPS are suitable for. Reasonably small (micrometer or smaller) spot sizes allow elemental mapping.

A major disadvantage of SIMS is that there is a very great range of ionization rates for different elements. Furthermore, the rates will vary depending on the other species present (matrix effects). Either a beam of positive or negative ions can be used as the exciting beam, although the response factors are m u c h different between them. The biggest differences are found with the very electronegative halogens and the electropositive alkali metals. The variability in response factors makes quantification very difficult and closely matched standards critical. Of use is ASTM E 1505, Guide for Determining SIMS Relative Sensitivity Factors from Ion Implanted External Standards. In SIMS, as in sputter profiling in Auger and XPS, there are other effects in addition to simply removing the surface atoms. For instance, there is implantation of the sputtering gas and a rearrangement or interfacial mixing of the surface layers. Also, compositional changes caused by preferential sputtering of one element versus another also occur. This is actually a bigger problem for Auger and XPS, which measure the surface, as compared to SIMS, which measures the elements ejected from the surface which soon reach an equilibrium with the actual composition. Static SIMS uses a much less intense ion beam than Dynamic SIMS. This gives the advantage of not destroying all the molecular species on the surface, which results in one being able to obtain significant chemical information from the surface. It also maintains the integrity of the surface during analysis so that it is much more of a surface technique than Dynamic SIMS. Time of Flight (TOF) SIMS refers to the mode of analysis of the ionized particles rather than their generation process. It provides a very wide mass range plus very high sensitivity.

OTHER SURFACE TECHNIQUES

The highly variable response factors that are the main limitation of SIMS are almost eliminated by Secondary Neutral

CHAPTER 4 - - S U R F A C E A N A L Y S I S
Mass Spectroscopies (SNMS), which provides relatively nonselective i o n i z a t i o n of the s p u t t e r e d species. S e p a r a t i n g the sputtering a n d ionizing functions of SIMS not only eliminates m a t r i x effects b u t also allows for m u c h less aggressive sputtering conditions. The h i g h e r cost of the systems is an inevitable trade-off. There are three ways that the s p u t t e r e d n e u t r a l species can be ionized. Surface Analysis by Laser Ionization (SALI) uses a high-power laser for p h o t o i o n i z a t i o n , while Glow Discharge Mass Spectroscopy ionizes the neutrals in a glow discharge plasma. The t h i r d m e t h o d is Electron I m p a c t Ionization, and it is labeled by the n a m e of the overall technique, SNMS. Both Electron I m p a c t SNMS and SALI can give SIMS-type inf o r m a t i o n on p o i n t defects w i t h o u t the quantification p r o b l e m s that SIMS is prone to. SALI is available with a time of flight (TOF) mass s p e c t r o m e t e r which is desirable if h i g h e r mass range a n d r e s o l u t i o n is n e e d e d t h a n can be p r o v i d e d by s t a n d a r d mass spectrometers. Rutherford Backscatter Spectroscopy (RBS) requires a monoenergetic b e a m of high-energy particles (helium ions) that is bounced off of the surface to be analyzed. By analyzing the energy of the backscattered particles, a standardless, nondestructive, quantitative depth profile of the top several m i c r o m e t e r s of the surface can be obtained. A related technique is Ion Scattering Spectroscopy (ISS) in which a lowenergy monoenergetic b e a m of ions is directed onto the surface and the energy of the scattered ions is measured. This technique is perhaps the most selective technique of all with regard to only analyzing the t o p m o s t layer of atoms. Its major limitations are that it is not able to detect elements at low concentration levels, and it has poor ability to discriminate between elements with similar atomic mass.

81

Spectrometer (EDS). Quantification can be quite good if appropriate standards are used. The X-ray detector can be set to only detect and count X-rays that have energies within a n a r r o w range. This output can then be used to generate elemental distribution maps, or line scans. Newer detectors with ultrathin windows can easily detect all elements with an atomic n u m b e r of 5 (boron) or greater. Some applications of SEM-EDS analysis are given in the metallography chapter of this manual. Particle Induced X-Ray Emission (PIXE) is similar to EDS analysis except that it uses high-energy particles instead of electrons to create the vacancies that lead to X-ray emission. It offers orders of magnitude better detection limits for trace elements than does EDS. Transmission Electron Microscopy (TEM) and Scanning Transmission Electron Microscopy (STEM) require extensive sample preparation. When coupled with another technique (EDS for example), they can be useful in determining the nature of surface films or in illuminating the microstructural causes of corrosion. Environmental Scanning Electron Microscopes (ESEM) that are equipped with EDS spectrometers allow SEM-EDS type data to be obtained from samples in the hydrated state. Fourier Transform Infrared Spectroscopy (FTIR) and Laser R a m a n Spectroscopy (LRS) provide complementary views of chemical bonding in a sample by studying the vibrational energies of the bonds. Surface Enhanced R a m a n Spectroscopy (SERS) can give vibrational spectra of in situ films. A useful review of the application of these vibrational spectroscopies is available [19].

IN SITU M E T H O D S
Because of the changes that can occur in preparing and analyzing surfaces for high-vacuum techniques, there is great interest in techniques that can obtain information as to the chemical state of metal surfaces while they are in aqueous environments. Some of the most exciting research on the fundamentals of corrosion are using these new techniques. Scanning Tunneling Microscopy (STM) a n d especially Scanning Force Microscopy (SFM) were the first techniques to give an atomic scale and three-dimensional (3-D) image of a surface that would p e r m i t observation in aqueous environments. Since the first scanning probe microscope was invented in 1981 by Gerd Binnig and Heinrich Rohrer, a whole family of scanning probe microscopies have evolved. All of these Scanning Probe Microscopies operate by scanning a small probe tip over the surface to be imaged and creating distributional maps of the response. Two of the most useful for corrosion science are Scanning Kelvin Probe Atomic Force Microscopy (SKPAFM) and Scanning Electrochemical Microscopy (SECM). Two valuable resources on these and other techniques are the Electrochemical Society's

N E A R SURFACE TECHNIQUES
Although not a true surface technique, SEM-EDS often provides useful information in regard to surface corrosion mechanism. The ubiquitous nature, low cost, and ease of use of this technique cause it to be used as a tool in m a n y failure analyses involving corrosion. Because its analysis depth is m u c h larger (approximately a micrometer) than the true surface techniques, it is not necessary to analyze samples that are high-vacuum compatible. This restflts in the necessity of almost no sample preparation for m a n y different kinds of samples. The sample is scanned with a high-energy (typically 5-30 KeV) electron b e a m in a raster pattern, which causes the ejection of a n u m b e r of particles including secondary electrons, backscattered electrons, and X-rays. Secondary electrons (with energies less than 50 eV) are only detectable if they are generated in the top surface of a sample; this causes the secondary electron output to be responsive to topographical detail and therefore gives an image that is r e m a r k a b l y similar to that seen with an optical microscope. Added advantages are greater magnification and depth of field. The contrast in backscattered electron images is mainly dependent on atomic number, so these images provide rough elemental distribution information. Element identification is provided by analysis of the characteristic X-rays that are emitted with an Energy Dispersive

Proceedings on the Symposium on Localized In Situ Methods for Investigating Electrochemical Interfaces [2] and Scanning Electrochemical Microscopy, which has been edited by Bair and Mirkin [20].
SECM is discussed elsewhere in this handbook. The Scanning Kelvin Probe is an updating and miniaturization of the classic method that was first postulated by Lord Kelvin in 1861. It is essentially a non-contact vibrating capacitor

82

CORROSION TESTS AND STANDARDS MANUAL

[6] Application of Surface Analysis Methods to Environmental/ Material Interactions, D. R. Baer, C. R. Clayton, and G. D. Davis, Eds., The Electrochemical Society, Inc., Pennington, NJ, 1991. [7] Surface Analysis--The Principal Techniques, J. C. Vickerman Ed., John Wiley & Sons, 1997. [8] Encyclopedia of Materials Characterization: Surfaces, Interfaces, Thin Films, C. R. Brundle, C. A. Evans, Jr., and S. Wilson, Eds., Butterworth-Heinemann, Boston, MA, 1992. [9] Powell, C. J., et al., "Methods of Surface Characterization,"

f o r m e d b e t w e e n t h e s a m p l e a n d a v i b r a t i n g electrode tip, w h i c h m e a s u r e s t h e w o r k f u n c t i o n of t h e sample. S i n c e t h e w o r k f u n c t i o n is e x t r e m e l y d e p e n d e n t o n s u r f a c e c o n dition, the SKP can be used to study such p h e n o m e n a as oxide layer imperfections, surface and bulk contamination, surface c h a r g i n g , etc. The a v a i l a b i l i t y of h i g h intensity, s y n c h r o n o u s X - r a y s o u r c e s at n a t i o n a l s y n c h r o t r o n c e n t e r s has a l l o w e d t h e d e v e l o p m e n t of a n u m b e r of n e w tools t h a t c a n study passive o r c o r r o s i o n films as t h e y are f o r m i n g in a q u e o u s env i r o n m e n t s . S u r f a c e X - R a y D i f f r a c t i o n (SXRD) p r o v i d e s a d i r e c t d e t e r m i n a t i o n of the crystal s t r u c t u r e of the a t o m s of t h e surface. S u r f a c e E x t e n d e d X - R a y A b s o r p t i o n F i n e S t r u c t u r e ( S E X A F S ) c a n p r o v i d e i n f o r m a t i o n on t h e geom e t r i c s t r u c t u r e of a t o m s w i t h i n a few a n g s t r o m s a r o u n d the a b s o r b i n g a t o m . These are truly exciting t i m e s for the application of surface analysis to c o r r o s i o n problems.

Beam Effects, Surface Topography and Depth Profiling in Surface Analysis, Vol. 5, Kluwer Academic Publishers, 1998. [10] Surface Characterization: A User's Sourcebook, D. Brune et al.,
Eds., John Wiley & Sons, 1997.

[11] Ion Spectroscopies for Surface Analysis, A. W. Czanderna and

D. Hercules, Eds., Plenum, New York, 1991.

[12] McIntyre, N. S. and Chan, T. C., "Uses of Auger Electa-on and Photoelectron Spectroscopes in Corrosion Science," Practical Surface Analysis, 2nd ed., Vol. A, Auger and X-Ray Photoelectron Spectroscopy, John Wiley & Sons Ltd., Chichester,
U.K., 1990.

REFERENCES
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