Review

Received: 9 December 2015 Revised: 15 March 2016 Accepted: 27 March 2016 Published online in Wiley Online Library: 2 May 2016

(wileyonlinelibrary.com) DOI 10.1002/xrs.2697 https://onlinelibrary.wiley.com/doi/epdf/10.1002/xrs.2697

Artificial peaks in energy dispersive X-ray

spectra: sum peaks, escape peaks, and
diffraction peaks
Ryohei Tanaka,a* Koretaka Yuge,a Jun Kawaia and Hussain Alawadhib
Sum peaks, escape peaks, and diffraction peaks are considered artificial or spurious peaks in energy dispersive X-ray spectrome-
try. Experimental examples are given, which showed that escape and diffraction peaks can add up to become sum peaks. These
artificial peaks are not weak, and great care must be taken to differentiate them from peaks due to impurity or trace elements.
The relationship between the intensity of a sum peak and the original peaks is illustrated using computer simulation as well as
probability theory. Copyright © 2016 John Wiley & Sons, Ltd.

Introduction
Sum peaks are often found in X-ray emission spectra such as X-ray
fluorescence (XRF) or scanning electron microscope-energy disper-
sive X-ray spectrometry [SEM-EDX (-EDS)]. When two photons are
incident upon an X-ray detector simultaneously, the electronic cir-
cuit cannot discriminate between the two pulses, and it will record
a single pulse. A peak appears at the energy corresponding to the
sum energy of two photons. The intensity of such a sum peak in-
creases as the number of photons impinging on the x-ray detector
is increased. Escape peaks are often found in EDX (EDS) spectra.
When X-ray photons interact with a Si solid state detector, they
can excite some Si atoms to emit characteristic Kα X-rays in the de-
tector. If these X-rays escape from the detector, instead of the orig-
inal photon energy, a peak appears at an energy lower by the Si Kα
energy in the X-ray spectrum. The intensity of the escape peak de-
pends on the shape, size, and arrangement of an X-ray detector. A
diffraction peak is observed when X-rays incident upon a large-size
single crystal is diffracted into the X-ray detector. Therefore, care
should be taken in X-ray fluorescence analysis of large-size single
crystal samples. The diffraction peaks can also appear in micro X-
ray fluorescence when using a capillary wave guide for the X-ray in-
cident beam, and thus causing difficulties in the analysis of samples
made up from micrometer-size crystals.
These three kinds of peaks are sometimes quite strong, and
therefore, care must be taken in energy dispersive X-ray fluores-
cence (ED-XRF) analysis when they are present. It has been pointed
out that for trace analysis, weak lines, such as X-ray Raman[1] or ra-
diative Auger satellites,[2,3] should be treated carefully. However
sum, escape, and diffraction peaks are three orders of magnitude
stronger than Raman or radiative Auger peaks.
Lead Lα line (10.55 keV) overlaps Arsenic Kα line (10.54 keV), and
when a mixture of Pb and As is analyzed, the Pb Lβ line (12.61 keV)
is used instead. However, the energy of Pb Lβ line is about twice the
energy of the iron Kα line (6.40 keV), and the sum peak of Fe Kα + Kα
overlaps Pb Lβ. Therefore, minor Pb and As in major Fe matrix, such
as soil and sediment, are quite difficult to quantify accurately. To
certify the quantitative analysis of these samples, the counting rate
should be deliberately low to eliminate the iron sum peak. In the JIS
(Japanese Industrial Standards) document,[4] iron Kα + Kα sum peak
intensity should be less than 1/1000 of iron Kα main peak
intensity[5] when using an ED-XRF spectrometer.
Although sum peak interference can greatly affect the accuracy
of X-ray analysis, the fundamental basis of sum peaks is not well
explained in text books. For example, Knoll[6] mentions that ‘For
n = 20,000 s
1 and an effective width of 5 μm, Eq. (17.7) predicts
that 90.5% of all intervals will be greater than this width. However,
two pulses are affected if a pile-up event takes place, so that only
about 81% of all true events escape pile-up and are properly
recorded.’ Another example is a report by Amekura et al.,[7] who
measured some weak lines in X-ray emission spectra and found
that their intensities changed with a change in the incident beam
intensity: the 0th peak (true events without pile up) is proportional
to the incident beam intensity, 1st peak (sum peak due to pile up of
two pulses) squarely proportional, 2nd peak (pile up of three pulses)
cubically proportional, and 3rd peak (pile up of four pulses) quadru-
ply proportional. They finally concluded that ‘these peaks are as-
cribed to the sum peaks of two, three and four X-ray photons …
enter the Si:Li detector in a very short period …’.
For the practical XRF analysis, the sum peaks of the major ele-
ments (e.g. Fe) interfere with the minor toxic elements (As and
Pb), and thus, it is important to know the sum peak intensity as a
function of the shaping time (i.e. energy resolution) as well as
counting rate (concentration of the major element or incident
beam intensity). The present work gives a short account of artificial
or spurious peaks in X-ray spectra.
* Correspondence to: Ryohei Tanaka, Department of Materials Science and
Engineering, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan. E-mail: tanaka.
ryohei.85z@st.kyoto-u.ac.jp
a Department of Materials Science and Engineering, Kyoto University, Sakyo-ku,
Kyoto, 606-8501, Japan
b Applied Physics Department, X-ray Center for Material Analysis, University of
Sharjah, United Arab Emirates
5

X-Ray Spectrom. 2017, 46, 5–11 Copyright © 2016 John Wiley & Sons, Ltd.
 Experiment
Figure 1 shows the XRF spectra for a Ge single crystal measured
by a Horiba XGT 7200 X-ray analytical microscope, equipped with
Rh anode X-ray tube, two single capillary X-ray guide tubes (spot
sizes of 1.2 mm and 50 μm), and a silicon drift detector.[8] The
tube voltages were (a) 15 kV and (b) 50 kV. Each channel was
set to 10 eV in X-ray energy. The sample current was 380 μA for
15 kV and 15 μA for 50 kV tube voltages, and the accumulation
time was 600 s. Many diffraction peaks can be seen in Fig. 1. It
is interesting to see the sum peak of a diffraction peak and the
Ge Kα in the 15 kV spectrum (e.g. Ge Kα + DP1). For the 50 kV
spectrum, the background is higher, and these sum peaks are
hidden. Therefore, it is important to watch not only for the sum
peaks of characteristic lines but also for the sum peaks of diffrac-
tion peaks.
Figure 2 shows the spectra for a GaP single crystal. The experi-
mental conditions were similar to Fig. 1, but details were different
and are shown in the inset of Fig. 2. The diffraction peaks can be
discriminated by a small rotation of the sample. It is remarkable
to observe the escape peak of a sum peak (e.g. 2× Ga-Kα-Esc).
Figure 3 shows the spectra for a ZnS single crystal with similar ex-
perimental conditions as Figs 1 and 2. The details are shown in the
inset of Fig. 3. The artificial peaks in these spectra are weaker than
those in Figs 1 and 2. But an interesting feature in this spectrum
is the peak around 0.57 keV. This peak is not due to the O-Kα, which

Figure 1. Fig. 1a (top) and b (bottom). X-ray fluorescence spectra of a Ge single crystal excited by Rh anode tube with an applied voltage of (a) 15 kV and (b)
50 kV. DP, diffraction peak; Esc, escape peak; and ‘+’ denotes a sum peak.
6

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Artificial peaks in energy dispersive X-ray spectra

Figure 2. Rh anode tube spectra of a GaP single crystal excited by Rh anode tube with an applied voltage of (a) 15 kV and (b) 50 kV. Peak labels are the same
as in Fig. 1.

the detector cannot measure. It is actually a Si escape peak for the
S-K line.[9,10]
Figure 4 shows synchrotron radiation (SR) XRF spectrum mea-
sured at SPring-8 by Nakai in his forensic report, which was submit-
ted to court for the arsenic murder case in Japan, but replotted by
Kawai.[11,12] Nakai did not plot the SR-XRF spectra clearly, but
Kawai[11,12] claimed faults in Nakai’s forensic report by replotting
the XRF spectra clearly, where all the escape peaks were assigned.
A Ge solid state detector was used in the experiment of Fig. 4. It
should be noted that the peaks in the soft X-ray region (less than
1 keV) were not true characteristic X-ray peaks, but artificial Ge es-
cape peaks. This is because the SR-XRF experiment was performed
in air. The energy difference between As Kβ (11.73 keV) and As Kβ
escape peak is the Ge Kα X-ray energy (9.87 keV). It should also be
noted that the sum peak of As-Kα + Kα can be seen around
21 keV and has a low energy tail, caused by a partial pile-up
phenomena.
Theory of sum peaks
In order to theoretically address the dependence of sum peaks on
the X-ray intensity, a simple model is considered where individual
pulses randomly enter the detector, and time resolution of the de-
tector is defined by r seconds. Here, incident pulses are all assumed
to be delta functions and the number of pulses per second, c, is
kept fixed. Under these conditions, an analytical expression for
the intensity as a function of c and r can be obtained as follows.
7

X-Ray Spectrom. 2017, 46, 5–11 Copyright © 2016 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/xrs
 Figure 3. Rh anode tube spectra of a ZnS single crystal excited by Rh anode tube with an applied voltage of (a) 15 kV and (b) 50 kV. Peak labels are the same
as in Fig. 1. Note that the peak around 0.57 keV is the S-K escape peak and not the Oxygen Kα line.

First, each second is uniformly divided into 1/r equal parts, as c

shown in Fig. 5, where each individual part is considered a ‘con- A ¼ ∑ c C n r n ð1
r Þc
n : (2)
tainer’ or ‘box’ that can capture multiple pulses within the time res- n¼0

olution of the detector. Then the intensity at the n-th peak (n = 1

Therefore, intensity ratio of the m-th sum peak to the main peak
corresponds to the zeroth-order peak, i.e., true events without pile
up, and n > 1 correspond to sum peaks), In, should be proportional is given by
to the probability to find n pulses in a single container when c inde-
pendent pulses are randomly distributed into 1/r containers: Imþ1 Pmþ1 c C mþ1 r mþ1 ð1
r Þc
m
1 ðcr Þm
¼ ¼ ≈ : (3)
I1 P1 c C 1 rð1
r Þ
c
1 ðm þ 1Þ!
PðnÞ ¼ A
1 c C n r n ð1
r Þ
c
n
: (1)
To obtain the last equation, typical conditions of c > > 1, c
Here, cCn denotes combination, i.e., the number of picking n un- > > m, and r < < 1 are taken. It is clearly seen that the intensity ra-
ordered pulses from c possibilities, and A is the normalization factor tio of the m-th sum peak is proportional to the m-th power of the
for the probability given by: number of pulses that entered in a unit time, which is consistent
8

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Artificial peaks in energy dispersive X-ray spectra

Figure 4. As2O3 synchrotron radiation X-ray fluorescence spectrum measured at SPring-8 by Nakai as a forensic report (replotted by Kawai). The peak below
1 keV is the As-Kα escape peak and not the Oxygen Kα line. Sb is an impurity element, and Pb is due to a beam collimator.

Figure 5. Schematic illustration of the model where individual pulses randomly enter a detector.

with the results of our Monte Carlo simulation in the next section, as
well as with those of experiments reported by Amekura et al.[7]
Computer simulation of sum peaks
In order to show the validity of the analytical expression given in Eq.
(3), a Monte Carlo simulation was performed according to the fol-
lowing procedure. c × 102 random numbers were generated, which
represented the pulses due to the incident X-ray photons for a pe-
riod of a hundred seconds. These pulses were assumed to be delta
functions. If q pulses arrived within the time interval of r seconds,
they were considered to be piled up (i.e. a pulse would be observed
that had q times the energy of a single pulse). Setting the value of c
to 102, 103, 104, 105, 106, and so on, and fixing the value of r at
2.5 × 10
6 (Fig. 6), the frequency distributions of the X-ray spectra
were then obtained. The r values correspond to the time resolution
or shaping time of the detector (2.5 μs). The simulation was per-
formed ten times for each value of c by generating the random
number series with ten different seed points. After averaging the
ten different iterations, the frequency distributions of the X-ray in-
tensity are shown in Fig. 6. As c became larger (e.g. the major ele-
ment concentration increased or the incident excitation beam
became stronger), the intensities of sum peaks increased.
The simulation was also performed for r = 5.0 μs in order to com-
pare with the main peak intensity estimated by Knoll in his
book.[6,13] Values of 90.6% and 82.3% are calculated for the main
peak intensities that escape pile up for r = 2.5 and 5.0 μs, respec-
tively. The second value is in good agreement with the value of
81% estimated by Knoll for r = 5.0 μs.[6,13] The physical meaning of
the ‘container’ width in the present work is 1/r, which is analogous
to the time constant of the exponentially decaying signal, I(t) = I0
exp(
rt), used by Knoll.
The ratio of the intensity of the m-th sum peak relative to the
main peak is proportional to cm, which is shown in Fig.7. This result
is consistent with the analytical expression that was obtained theo-
retically in the previous section and also with the experimental re-
sults of Amekura et al.[7]
Summary
Sum peaks are due to a pile up of two or more electric pulses. These
peaks involve not only characteristic lines but also escape peaks
and diffraction peaks, as were shown in several examples. Sum
peak intensity depends on the time resolution of the X-ray detector,
including the electric circuits. When the shaping time of the electric
circuit is set to larger values, the energy resolution of the spectra be-
comes better, but the time resolution becomes worse. They are in-
versely related, and this can cause difficulties in some applications.
The analytical expression of the dependence of sum peak intensity
on incident pulses and time resolution was derived and verified its
validity based on Monte Carlo simulation. The intensity of m-th sum
peak is proportional to the m-th power of the number of incident
9

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 2 3 4 5 6
Figure 6. Sum peak X-ray spectra for (a) 10 , (b) 10 , (c) 10 , (d) 10 , and (e) 10 cps (counts per second) X-ray intensity and a shaping time of r = 2.5 μs.

pulses and resolution rate, which therefore means that the shaping
time of the detector electric circuit or digital signal processor and
the X-ray tube voltage and current must be set carefully to lower
the counting rate in order to avoid the sum peaks. However, those
are still strong enough for detecting the minor elements.

Acknowledgements
Thanks are due to Professor I. Kanno of Kyoto University for his fruit-
ful discussion.

References
Figure 7. The relation between the number of pulses (c) and the relative
intensity of the m-th sum peak with respect to the original peak (I1). The
slopes of the solid and dashed lines are 0.98 and 1.84, respectively, which
are approximately 1 and 2. The differences are due to a partial pile-up
10
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