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2.1.7
Ultraviolet Photoelectron Spectroscopy (UPS)
2.2
Auger Electron Spectroscopy (AES)
After XPS, AES is the next most widely used surface-analytical technique. As an ac-
cepted surface technique AES actually predates XPS by two to three years, because
the potential of XPS as a surface-specific technique was not recognized immediately
by the surface-science community. Pioneering work was performed by Harris [2.125]
and by Weber and Peria [2.126], but the technique as it is known today is basically
the same as that established by Palmberg et al. [2.127].
2.2 Auger Electron Spectroscopy (AES) 33
2.2.1
Principles
2.2.2
Instrumentation
As in the CHA, therefore, scanning the deflection potential ±V and recording the sig-
nal as a function of electron energy provide the distribution in energy of electrons
leaving the sample surface.
If the angular spread of the acceptance angle is Da, the relative energy resolution of
a CMA is:
where w is the effective slit width. For typical angular spread Da & 68, w can be re-
placed by the source size (i. e. the area on the sample from which electrons are ac-
cepted). The source size is very small, because of the focused primary beam, and the
important property of the CMA is, therefore, its very high transmission, arising from
the large solid angle of acceptance; for Da & 68, transmission is approximately 14 %.
Conventionally, Auger spectra are presented in the differentiated energy distribution
form dN(E)/dE, rather than in the undifferentiated form N(E) used in XPS. Differ-
entiating enhances the visibility of Auger features, as is demonstrated in Fig. 2.20, in
which the differentiated spectrum from boron is shown above the corresponding
N(E) spectrum. The N(E) distribution is nowadays recorded digitally, and differentia-
tion is performed by computer. With the rapid improvement in the signal-to-noise
2.2.3
Spectral Information
As stated above, the range of primary energies typically used in conventional AES is 3±
10 keV, and the ionization cross-section passes through a maximum at 3±5 times the
binding energy of an electron in the ionized core level. The core levels that can be io-
nized efficiently are, therefore, limited. Thus K-shell ionization efficiency is adequate
up to Z & 14 (silicon), L3 up to Z & 38 (strontium), M5 up to Z & 76 (osmium), and so
on (for the much higher primary energies used in SAM, the ranges are correspond-
ingly extended). This means that in various regions of the periodic table, characteristic
Auger transitions occur that are most prominent under typical operating conditions.
Figures 2.21±2.23 show some of these prominent Auger features, all recorded using
a CMA, in the differential distribution [2.129]. Examples of the KLL Auger series are
shown in Fig. 2.21, of the LMM series in Fig. 2.22, and of the MNN series in
Fig. 2.23. In the KLL series the most prominent feature is a single peak arising from
the KL2,3L2,3 transition, with minor features from other Auger transitions to lower
energy. The LMM series is characterized by a triplet arising from L3M2,3M2,3,
L3M2,3M4,5, and L3M4,5M4,5, transitions in ascending order of kinetic energy, with an-
other intense peak, the M2,3M4,5M4,5, appearing at very low energy (e. g. 50 eV for
iron). Note that AES transitions involving electrons in valence band levels are often
written with a V rather than the full symbol of the level. Thus L3M2,3M4,5 and
2.2 Auger Electron Spectroscopy (AES) 37
Fig. 2.21. KLL Auger series characteristic of the light elements [2.129].
Fig. 2.23. MNN Auger series in the second series of transition elements [2.129].
L3M4,5M4,5 would often appear as L3M2,3V and L3VV, respectively, and similarly
M2,3M4,5M4,5, as M2,3VV. In Fig. 2.22 the increase in the intensity of the L3VV peak
relative to the other two, upon going from chromium to iron, is because of the pro-
gressive increase in the electron density in the valence band. The characteristic doub-
let seen in the MNN series arises from the M4,5N4,5N4,5 transitions, in which the
doublet separation is that of the core levels M4 and M5.
Chemical effects are quite commonly observed in Auger spectra, but are difficult to
interpret compared with those in XPS, because additional core levels are involved in
the Auger process. Some examples of the changes to be seen in the KLL spectrum of
carbon in different chemical environments are given in Fig. 2.24 [2.130]. Such spec-
tra are typical components of data matrices (see Sect. 2.1.4.2) derived from AES
depth profiles (see below).
2.2 Auger Electron Spectroscopy (AES) 39
Associated with prominent features in an Auger spectrum are plasmon energy loss
features that are also found associated with photoelectron peaks in an XPS spec-
trum. Plasmon energy losses arise from excitation of modes of collective oscillation
of the conduction electrons by outgoing secondary electrons of sufficient energy.
Successive plasmon losses suffered by the back-scattered primary electrons can be
seen in both the N (E) and the dN (E)/dE spectra of Fig. 2.20, from boron. The same
magnitude of plasmon loss, ~27 eV, is also associated with the KLL Auger peak of
boron. Plasmon losses are also present in Figs 2.21±2.24, but they are difficult to dis-
entangle from minor Auger features.
40 2 Electron Detection
Another type of loss feature not often recorded in Auger spectra can also be seen in
Fig. 2.20, in the dN(E)/dE spectrum at 810 eV. This type arises from core-level ioniza-
tion and forms the basis for the technique of core electron energy-loss spectroscopy
(CEELS). A primary electron interacting with an electron in a core level can cause exci-
tation either to an unoccupied continuum state, leading to complete ionization, or to
localized or partly localized final states, if available. Because the primary electron need
not give up all its energy in the interaction, the loss feature appears as a step in the sec-
ondary electron spectrum, with a tail decreasing progressively to lower energies. Dif-
ferentiation, as in Fig. 2.20, accentuates the visibility. In that figure, the loss at 810 eV
corresponds to the K-shell ionization edge of boron at approximately 190 eV.
2.2.4
Quantification and Depth Profiling
2.2.4.1 Quantification
If ionization of a core level X in an atom A in a solid matrix M by a primary electron
of energy Ep gives rise to the current IA(XYZ) of electrons produced by the Auger
transition XYZ, then the Auger current from A is
A l M (EA) cos y
IA (XYZ) = Ks (Ep , X) [1 + rM (E, a)] N (2.13)
A
N I A
1 r A lA R1
A
(2.15)
N1
A I1
A
1 r M lM RM
because the ionization cross-section, s, is the same for both standard and sample.
Then, as in XPS, assuming nearly equal roughness factors R A? & RM, Eq. (2.15) can
be reduced to:
A = SA IA
N (2.16)
where:
1
1 r A lA
N A
SA (2.17)
I1
A
1 r M lM
[2.133] and by Mroczkowski and Lichtman [2.134] for differential Auger spectra, and
for the direct, undifferentiated, spectra by Sato et al. [2.135]. A comprehensive dis-
cussion of the assumptions and simplifications involved and the corrections that
should be applied is given elsewhere [2.9, 2.136]. Although modern Auger spectro-
meters detect the spectra in the undifferentiated mode, many workers still evaluate
the spectra in the subsequently electronically differentiated mode, i. e. using peak-to-
peak heights, so that changes in peak shape as a result of changes in chemical bond-
ing are not taken into account and quantification in AES is still not as accurate as
that in XPS.
2.2.5
Applications
Like XPS, the application of AES has been very widespread, particularly in the earlier
years of its existence; more recently, the technique has been applied increasingly to
those problem areas that need the high spatial resolution that AES can provide and
XPS, currently, cannot. Because data acquisition in AES is faster than in XPS, it is
also employed widely in routine quality control by surface analysis of random sam-
ples from production lines of, for example, integrated circuits. In the semiconductor
industry, in particular, SIMS is a competing method. Note that AES and XPS on the
one hand and SIMS/SNMS on the other, both in depth-profiling mode, are comple-
mentary, the former gaining signal from the sputter-modified surface and the latter
from the flux of sputtered particles.
much higher than in the bulk, and the cohesive energy of the boundaries can be so
altered that the material becomes brittle. Knowledge of the nature of the segregating
elements and their grain boundary concentrations as a function of temperature can
be used to modify fabrication conditions and thereby improve the strength perfor-
mance of the material in service.
Goretzki [2.137] has discussed the importance and analysis of internal surfaces such
as grain boundaries and phase boundaries, and given several examples. He empha-
sizes that to avoid ambiguity in interpretation of the analysis, the internal surfaces
must be exposed by fracturing the material under UHV conditions inside the elec-
tron spectrometer. If this is not done, atmospheric contamination would immedi-
ately change the surface condition irrevocably. One of the examples from Goretzki's
paper is given in Fig. 2.26, in which Auger spectra in the differential mode from frac-
ture surfaces in the embrittled (Fig. 2.26A) and unembrittled (Fig. 2.26B) states of a
12 % Cr steel containing phosphorus as an impurity, are compared.
Embrittlement occurs when the steel is held at 400±600 8C for a long time. Note in
the spectrum from the embrittled material not only is the phosphorus concentration
greatly enhanced at the grain boundary, but the amounts of chromium and nickel,
relative to iron, are also increased. By setting the analyzer energy first to that of the
phosphorus peak, and then to that of the principal chromium peak, Auger maps
could be recorded showing the distribution of phosphorus and chromium over the
fracture surface. The two maps showed high correlation of the two elements, indicat-
ing association of phosphorus and chromium at the grain boundary, possibly as a
compound. Other recently published studies of the same 12 % steel have reported
enhanced phosphorus levels at the grain boundaries of the embrittled material
[2.138, 2.139]; similar results have been obtained for other high-chromium steel al-
loys [2.140, 2.141]. Reichl et al. [2.142] investigated the temperature-dependence of
surface segregation of S and N in a-Fe. In an initial phase, S diffusion occurred at
the grain boundaries and displaced N at the surface at higher temperatures. Other
Fig. 2.26. Auger spectra from fracture surfaces of a 125 Cr steel [2.137].
(A) embrittled state, (B) unembrittled state.
44 2 Electron Detection
applications in the study of grain boundary segregation in metals have included the
effects of boron, zirconium, and aluminum on Ni3Al intermetallics [2.143], the seg-
regation of phosphorus and molybdenum to grain boundaries in the superalloy Ni-
monic PE 16 as a function of aging treatment [2.144], and the enrichment of chro-
mium carbide and chromium±iron carbide at the grain boundaries in steel [2.145].
Application of AES to zirconia ceramics has been reported by Moser et al. [2.146].
Elemental maps of Al and Si demonstrate the grain boundary segregation of small
impurities of silica and alumina in these ceramics.
SAM) and TEM. An Auger electron spectrometer with high spatial resolution ima-
ging capability was developed especially for the detection of small particles and de-
fects which might be present in the ULSI regime; this enabled the inspection of wa-
fers up to 200 mm in diameter [2.150].
AES has also been applied to study preferential sputtering of TiSix forming for low-
resistivity conductor films in ULSI devices [2.151], or the electromigration behavior
of Au±Ag films on SiO2 using AES, XPS and AFM [2.152].
Fig. 2.28. Depth profiles of a Ti±diamond layer 4 h [2.153]. Auger line shapes of (C) Ti LM1M4
(A) before and (B) after annealing at 600 8C for and (D) C KLL at various depths.
(Sect. 2.1.6.6). The extent of interaction and interdiffusion can be established by AES
with depth profiling, although chemical information is normally absent, but the de-
velopment of the interface is usually studied by continuous recording of Auger spec-
tra during film deposition.
Zhu et al. [2.153] deposited Ti or Cr layers on diamond samples. The Ti±diamond or
Cr±diamond specimens were annealed at 600 8C for 4 h during metallization.
Figs 2.28 A and B show the depth profiles before and after annealing of a Ti/dia-
mond specimen, and Figs 2.28 C and D show the Ti LM1M4 Auger line shapes in the
N (E) mode and the C KLL line shape in the differentiated dN (E)/dE mode at differ-
ent depths. The unstructured Ti signal at the surface can be attributed to TiO2, be-
cause of smooth oxidation of the surface. But the greatest part of the layer consists of
TiC. The formation of TiC is also recognizable by the strongly structured carbon line
which changes its shape with depth and changes gradually into that of diamond. All
these features are consistent with the presence of TiC, indicating complete metalliza-
tion.
2.2 Auger Electron Spectroscopy (AES) 47
Other interesting thin-film studies using AES have included the growth of platinum
on TiO2- and SrO-terminated (100) SrTiO3 single-crystal substrates [2.154], of epitax-
ial niobium films on (110) TiO2 [2.155], the interaction of copper with a (0001) rhe-
nium surface [2.156], and the characterization of radio-frequency (rf) sputtered TiN
films on stainless steel [2.157].
A multilayer-type structure probably due to cords in the molten zone between single
arc sprayed (0.25 MPa) Ni droplets and steel substrate were found in AES point
depth profiles [2.158]. That particular arc spraying condition turned out to yield the
best adhesion. Plasma-sprayed Al2O3 layers separated from pre-oxidized Ni Sub-
strate had a micrometer-thick NiO layer on the substrate-sided face and micrometer-
deep oxide interdiffusion [2.159]. In this work also, AES point depth profiling sub-
stantiated technological assumptions about adhesion mechanisms.
2.2.6
Scanning Auger Microscopy (SAM)
If an incident electron beam of sufficient energy for AES is rastered over a surface in
a manner similar to that in a scanning electron microscope (SEM), and if the analy-
zer is set to accept electrons of Auger energies characteristic of a particular element,
then an elemental map or image is again obtained, similar to XPS for the Quantum
2000 (Sect. 2.1.2.5).
This is illustrated in Fig. 2.30 [2.167]. The surface was that of a fractured compact of
SiC to which boron and carbon had been added to aid the sintering process. The aim
of the analysis was to establish the uniformity of distribution of the additives and the
presence or absence of impurities. The Auger maps show not only very non-uniform
distribution of boron (Fig. 2.30 a) but also strong correlation of boron with sodium
(Fig. 2.30 c), and weaker correlation of boron with potassium (Fig. 2.30 b). Point ana-
lyses for points A and B marked on the images reveal the presence of sulfur and cal-
2.2 Auger Electron Spectroscopy (AES) 49
cium in some areas also. In this instance the sintering process had not been opti-
mized.
Dedicated scanning auger microscopes with ultimate spatial resolution have been de-
veloped towards smallest possible spot size and still acceptable Auger signal-to-noise
ratio obtained within tolerable acquisition time. Electron guns used for SAM employ
electromagnetic focusing. Because focusing electrons of low energy into a small spot
is difficult, energies used in SAM are in the range of 25±50 keV, with beam currents of
the order of 1 nA or less and minimum spot size of approximately 15 nm.
2.3
Electron Energy-loss Spectroscopy (EELS)
Reinhard Schneider