SURFACE AND INTERFACE ANALYSIS

Surf. Interface Anal. 27, 1114–1117 (1999)

SHORT COMMUNICATION

Notes on Locating Peak Energies in XPS

János Végh*
Institute of Nuclear Research of the Hungarian Academy of Sciences, H-4001 Debrecen, Pf. 51, Hungary

The algorithms proposed for determination of the position in XPS are analysed. The method of bisected
chords is reformulated in a form readily available for digital-computers, another derivation of fitting a
parabola to the top of peak is given and some more non-iterative methods are presented. The suggested
methods determine different characteristics of the photopeak, such as ‘peak location’, maximum height,
centre of gravity and the distribution parameter. Copyright  1999 John Wiley & Sons, Ltd.
KEYWORDS: peak location; peak position; energy calibration; bisected chord method

INTRODUCTION Because of this, it is quite difficult to compare this method

with the present-day digital computer methods available
in the data evaluation software. Now we will reformulate
One of the key points in electron spectroscopy is to deter- it in a form readily available for use on the modern digital
mine the energy of the photo-peaks. Because the energy computers.
scale calibration itself is also based on the determination In this method chords are drawn horizontal (formerly
of the energies of some photopeaks, it is worth compar- parallel to the baseline). They intersect the irregular poly-
ing the features of the available methods offered for that gon, forming the peak envelope. Using the notation shown
purpose. in Fig. 1 for the kth chord (drawn at height yk ) it happens
between points .i, i C 1/ and .j, j C 1/. The E coordinates
of this chord are
METHODS USED TO LOCATE PEAKS yk yi.k/
Ek,L D Ei.k/ C [Ei.k/C1 Ei.k/ ] .1/
yi.k/C1 yi.k/
Let us have a measured spectrum y.E/ (a distribution
of counts y as a function of energy E), i.e. y.k/ is the and
number of counts recorded in channel k of nominal energy yk yj.k/C1
E.k/ . One can determine ‘peak position’ with several Ek,R D Ej.k/C1 [Ej.k/C1 Ej.k/ ] .2/
methods, each providing a different result, partly because yj.k/ yj.k/C1
a different characteristic is interpreted as a ‘peak position’.
In addition, different parts of the peaks are used in the for the left (L) and right (R) intersections, respectively,
calculation, i.e. the peaks are truncated differently. As with the two polygon sections.
Hansen indicates in his work determining peak position Usually, the data points are equidistant (i.e. E D
with a high precision,1 the arbitrary choice of the channels Ei.k/C1 Ei.k/ D Ej.k/C1 Ej.k/ ), so the energy of the
considered distorts the sample (which should be infinitely midpoint is
wide) and necessitates what in statistical language is called 
1
a ‘bias correction’. Also, it is worth noting that the so- Ek D Ei.k/ C Ej.k/C1 C E
called ‘binning’ (the non-infinitely small channel width) 2
can also distort the derived result (see section II. C.  
yk yi.k/ yk yj.k/C1
in Ref. 2). ð .3/
yi.k/C1 yi.k/ yj.k/ yj.k/C1

The bisected chord method
The method was originally given3 in terms like
plot spectra through . . . , draw the baseline,
. . . draw horizontal chords, etc.
* Correspondence to: J. Végh, Institute of Nuclear Research of the
Hungarian Academy of Sciences, H-4001 Debrecen, Pf. 51, Hungary.
E-mail: J.Vegh@atomki.hu
Contract/grant sponsor: Hungarian Academy of Sciences; Con-
tract/grant number: OTKA (T026514).
CCC 0142–2421/99/121114–04 $17.50
Copyright  1999 John Wiley & Sons, Ltd.
The same calculation can be carried out on several chords,
each contributing a midpoint energy. These midpoints are
then extrapolated to a value at the peak giving the peak
energy; in other words, a curve (line) is drawn through the
midpoints, which is some kind of (rather arbitrary) fitting.
As found by Cumpson,5 a simple average can be taken for
symmetrical peaks but the midpoints will scatter on both
sides of this line.
Without loss of generality, one can correct the calcu-
lated midpoint energy of a chord with an arbitrary constant
value, namely with the value (relative to the projected
peak energy) of the intersection of this fitted line and
the chord. After having corrected the individual Ek items,
Received 30 June 1999
Revised 23 August 1999; Accepted 23 August 1999
 LOCATING PEAK ENERGIES IN XPS
Figure 1. The notations used in the bisected chord method.
the energy of the peak itself is calculated as an average
of these corrected E0k values over all k chords, i.e. the
algorithm simplifies to a simple summation over properly
selected pairs of sections of the polygon. The sum can be
separated into two terms
X of the counts in adjacent channels will decrease sharply
[E0i.k/ C E0j.k/C1 ]
ED k
X as neighbouring peaks, asymmetric shape, etc), thus an
2 1
k more uncertainty. This analysis supports the suggestion
X  yk yi.k/ yk yj.k/C1
 from practical experience that this algoritm should use
yi.k/C1 yi.k/ yj.k/ yj.k/C1
C E k X .4/
2 1
k
The first sum is evidently the (unweighted) average energy
for all points used, whereas the second term needs more
attention. One can assume (without loss of generality) that
the symmetric peak is located symmetrically (i.e. such
that its peak energy Eo coincides with the nominal energy
of one of the measured points Ei ). Notice that in the
absence of statistical disturbance the individual terms in
the second sum would be exactly zero. It does not hold
for asymmetric peaks, so the second term measures the
asymmetry of the peak. This asymmetry can arise from the
asymmetric placing or the asymmetric shape of the peak,
or both. Of course, the counting statistics also affect these
terms, but in a statistical sense they remain valid.
The result above points to one more requirement: we
cannot select the chords arbitrarily. When drawing chords
at some equidistant heights, some measured points might
be used in calculating the midpoints for more than one
chord (or just the opposite: it might not be used at
all), which means that some measured points are used
more than once in calculating E, and the peak energy
becomes biased. According to the mathematical statistics,
one cannot use any of the four points used in evaluating
E.k/ , E.kC1/ or E.k 1/ . However, in practice one cannot be
so strict. For example, in spectra published by Powell4
only nine points fall in the [100%, 84%] height interval,
so only (maximum) two such chords could be derived.
When drawing statistical conclusions, we have to bear
this fact in mind.
Notice that the way the chords are drawn affects
the final result. The linear interpolation used above for
approximating the upper part of the distribution seems
reasonable and the need for some spline or other fitted
Copyright  1999 John Wiley & Sons, Ltd.
1115
envelope does not arise. It is easy to see that if the abso-
lute value of the slopes of the linear sections [i, i C 1] and
[j, j C 1], respectively, are different (and of course they
are), the resulting midpoint energy Ek will depend on the
actual value of yk , so the sampling frequency and range
should be given in the algorithm. An alternative could be
to start at the maximum height plus the two neighbour-
ing points and then extend the region on either side until
the new point allows a new chord. In this case yk could
be the middle height of the narrower height interval: for
example, in Fig. 1 yk D .yi C yj //2. The final resulting
peak energy could be derived as the energy coordinate
of the point where the line, fitted to the chord midpoints,
intersects the peak envelope.
Considering the uncertainty of E, it can be seen easily
that the closer the points are to the peak maximum, the
closer the counts in the adjacent channels are to each
other, i.e. their contribution to the uncertainty is greater.
This fact suggests that care be used when determining the
peak energy that the midpoints are extrapolated to. On
the other hand, although the uncertainty of E improves
with the number of the terms averaged, the difference
and so also will the influence of systematic errors (such
increase in the number of the chords will result in much
only points in the [100%, 84%] height interval.
In summary, the method is equivalent to the unweighted
average of the energies Ek , where the method of selecting
the points in summing greatly improves the precision,
focusing the summing to the points near to the peak
maximum, so that practically the maximum of the peak
height is evaluated as the peak location.
Non-iterative fitting methods
These methods rely heavily on the measured points being
equidistant, so in this section Ei stands for the sequence
number i. Note that in calculating the value of the trans-
formed function, at some point the neighbours of the point
are used; thus, in calculating the uncertainty, special care
should be taken so as not to use multiple data points.
Parabola fitting. A method for fitting a parabola (of the
form yi D aE2i CbEi Cc) to the top of the peak is described
by Cumpson et al.5 Another simple derivation of the same
result can be given using a transformation and a non-
iterative linear fitting. Let us consider the top few points
of the peak and transform the intensities as
Q.Ei / D yiC1 yi 1 .5/
This leads to
Q.Ei / D 4aEi C 2b .6/
i.e. the transformed function is linear in energy. To this
transformed function a straight line can be fitted (using
the weights Wi D [.yiC1 /2 C .yi 1 /2 ] 1 ), as described in
standard textbooks.6 The fitting results in the peak position
b
Eo D .7/
2a
Surf. Interface Anal. 27, 1114–1117 (1999)
1116 J. VÉGH

in full accordance with Eqn (14) of Ref. 5. From this the individual data points and calculate the parameters
derivation it is also clear immediately that the constant of the peak from the parameters of this linear function.
term c of the parabola (corresponding to a constant back- Because these methods can also be used to set up the
ground) does not have any role: however, a sloping back- other initial parameters (FWHM and height) for (at least
ground will shift the peak position. relatively) separated peaks, the further steps necessary to
derive them are also described there.
Polynomial fitting. A more generalized fitting procedure For a Gaussian of the form
can be derived easily. Having equidistant points, let us fit "  #
to the point with maximum height plus 2m neighbouring E i Eo 2
y.Ei / D yo exp p .11/
points an nth order polinom of the form 2
X
n
the transformation is7
fj D bnk jk .8/
kD0 Ei Eo
Q.Ei / D ln..yi 1 //.yiC1 // D 2 .12/
2
in such a way that
!2
For a Lorentzian of the form
X
Cm X
Cm X
n
yo
MD .fj yj /2 D bnk jk yj .9/ y.Ei / D   .13/
jD m jD m kD0
Ei Eo 2
1C
0.5
is minimum. The corresponding condition is
the transformation is8
∂M X
n X
Cm X
n X
Cm

D2 bnk jkCr 2 yj jr D 0 .10/ 1 1 16

∂bnr Q.Ei / D D .Ei Eo / .14/
kD0 jD m kD0 jD m yiC1 yi 1 yo 2

for r D 0, . . . , n. After changing the order Pof the summa- Three-point Gaussian method. Another quick and simple
tion and introducing the notations S D
Cm
kD m i
kCr
and method was proposed recently by Li et al.9 Three mea-
PCm rCk
sured points are used in the calculations, where the peak
Fr D rD m yi jr , one arrives at the system of equations
of the form energy is calculated as
X n
 2 2 
bnk SrCk D Fr E Eo E2 E2 E2 E2
ln yi j Ð yo i j Ð yj o i
kD0 1
ED   .15/
Because SrCk  0 for odd values of r C k, then when 2 ln yiEj Eo Ð yoEi Ej Ð yjEo Ei
fitting a second-order polynomial to the top five points of
the peak, i.e. n D 2 and m D 2, the system simplifies to where Ei , yi , Ej and yj are as shown on Fig. 1, and Eo
and yo denote the energy and height, respectively, of the
b20 S0 C b22 S2 D F0 point with the highest count.
b20 S2 C b22 S4 D F2
The moments method
b21 S2 D F1
It is worth drawing attention to the momentum method
and the coefficients of the parabola are readily available. too. In this method2 the moments of the distribution y.E/
are used. The ith moment is defined as the expectation
Fitting Gaussian and Lorentzian. Note that fitting a parabola value of Ei . The peak position will be the first central
to the top of the peak essentially corresponds to expanding moment (see Eqn (9) in Ref. 2: the simple weighted
the lineshape as a Taylor series by .E Eo /, neglecting the average of the spectrum data points is taken)
third- and higher order terms. Obviously, only the very top
of the peak is similar to a parabola, so a real lineshape can X
Ek y k
be more effectively approximated with either a Gaussian
or a Lorentzian. Although the peaks in the XPS are neither ED X
k
.16/
purely Lorentzian nor Gaussian, they are much closer to yk
either of the two than to a parabola. Because of this, much k

more of the peak (unlike the top few per cent of the peak at for some points near to the peak energy. To calculate the
the parabola fitting) can be used in the calculation, although statistical uncertainty of E we also need to calculate the
the fitting region is usually limited to the points whose second central moment (see Eqn (11) in Ref. 2) and obtain
contents are greater than half-maximum.
It is a well-known fact that—similar to the parabola fit- X 
E2k yk
ting—the frequently used Gaussian and Lorentzian peak  k 2
shapes can also be linearized, i.e. peak parameters such  X E
 
as position can be calculated non-iteratively. The trick is yk
again the same as at fitting the parabola: using the equidis-  2 .E/ D k
X .17/
tant nature of the recorded spectra, transform the function yk
into a linear function using the immediate neighbours of k

Surf. Interface Anal. 27, 1114–1117 (1999) Copyright  1999 John Wiley & Sons, Ltd.
 LOCATING PEAK ENERGIES IN XPS 1117

Note that the calculated centre of gravity E is indepen-
dent of the actual shape of the symmetric distribution. The
method is a well-established mathematical technique, sim-
ple enough to use even on hand-held calculators and can
be included readily in evaluation software. However, as
Hansen points out in his work for determining the peak
position with high precision,1 when using a truncated
line to estimate the correct line position a bias correction
should be applied. Under the conditions used in the energy
calibration measurements, this correction is of the order
of 2–5 meV.
Acknowledgements
The author kindly acknowledges Dr C. J. Powell for providing the
measurement data used in his work.4 The support of Hungarian grant
OTKA (T026514) is kindly acknowledged.

REFERENCES

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5. Cumpson PJ, Seah MP, Spencer SJ. Surf. Interface Anal.
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6. Bevington PR. Data Reduction and Error Analysis for the
Physical Sciences (McGraw-Hill, New York, 1969) Ch. 6.
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8. Mukoyama T, Végh J. Nucl. Instrum. Methods 1980; 173:
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Copyright  1999 John Wiley & Sons, Ltd. Surf. Interface Anal. 27, 1114–1117 (1999)