X-RAY SPECTROMETRY

X-Ray Spectrom. 2001; 30: 49–55

Efficiency calibration of energy-dispersive detectors for

application in quantitative x- and g-ray spectrometry
I. Szalóki,1∗ S. Szegedi,1 K. Varga,2 M. Braun,3 J. Osán4† and R. Van Grieken4
1
Institute of Experimental Physics, University of Debrecen, Bem tér 18/a, H-4026 Debrecen, Hungary
2
Department of Radiochemistry, University of Veszprém, P.O. Box 158, H-8201 Veszprém, Hungary
3
Department of Inorganic Chemistry, University of Debrecen, P.O. Box 21, H-4010 Debrecen, Hungary
4
Department of Chemistry, University of Antwerp (UIA), Universiteitsplein 1, B-2610 Antwerp, Belgium

Received 27 July 2000; Accepted 8 November 2000

A semi-empirical method was used in a full-peak efficiency calculation procedure; it was based on the
measurements of characteristic x-ray lines of pure elemental and compound samples and on the application
of the fundamental parameter method (FPM) for the theoretical calculation of the characteristic x-ray
intensities. Radioactive standards were applied for the efficiency calibration of different semiconductor
detectors [Si(Li), Si-PIN and HpGe]. The efficiency curves were fitted to the characteristic intensities
measured by a conventional Si(Li) and two Si-PIN detectors, using 125 I and 55 Fe radioactive sources for
x-ray excitation in a ring-shaped geometrical arrangement. Several quantitative applications in x- and
g-ray spectrometry were carried out with these calibrated detectors: (i) x-ray fluorescence (XRF) analysis of
sediment samples [Si(Li)], (ii) determination of specific activity of 137 Cs nuclide in sediment core samples
originated from an oxbow area of the river Tisza, using g-spectroscopy (HpGe) with low-background
conditions, (iii) study of electrosorption phenomena at solid–liquid interfaces by making use of an in
situ radiotracer method based on the application of low-energy x-ray emitting radionuclides (e.g. 65 Zn),
(iv) quantitative XRF analysis of ceramic glaze and (v) electron microprobe analysis of aerosol particles
using an instrument equipped with a thin-window Si(Li) detector. Copyright  2001 John Wiley & Sons,
Ltd.

INTRODUCTION and easily executable procedure should be developed in

order to avoid the use of calibrated radioactive sources. On
Applications of semiconductor detectors for the quantitative
the other hand, the lack of radioactive isotopes that emit
determination of the elemental composition of environmen-
enough low-energy x-ray lines and have a long half-life lim-
tal samples are based on the measurement of characteristic
its strongly the applicability of this empirical method. In
x-ray emission and the natural radioactivity of samples.
x-ray fluorescence (XRF) analysis, the so-called fundamental
These analytical tasks require the exact knowledge of the
parameter method (FPM) offers a well-defined mathemati-
physical parameters of the applied energy-dispersive (ED)
cal relationship between characteristic x-ray intensities and
detectors, namely the full-energy peak efficiency function.
concentrations of analysed elements and this provides an
For this reason, several semi-empirical calibration methods
opportunity for calibrating the efficiency function and deter-
applying radioactive standards for approximating unknown
mining the critical parameters of the semiconductor x-ray
structural parameters of both Si(Li) and Ge detectors have
detector. In this paper, we present a semi-empirical calibra-
been published, as reviewed by Campbell and McGhee.1
tion and calculation procedure which is based on measure-
The general procedure implies measuring the intensities
ments of the characteristic intensities of pure element and
of radionuclide lines with an accurately known emission
compound standard samples and on application of the FPM
rate covering the 5–1000 keV energy range for x- and -
technique for conventional Si(Li) and Peltier-cooled Si-PIN
rays. However, in a common laboratory, an appropriate set
detectors. It is obvious that knowledge of the physical param-
of calibrated radioactive standards is generally not avail-
eters of an ED detector, which are frequently not available,
able for practical applications, and therefore a simplified
is necessary to construct an accurate efficiency calibration.
Ł Correspondence
Therefore, most semi-empirical methods1,2 are based on the
to: I. Szalóki, Institute of Experimental Physics,
University of Debrecen, Bem tér 18/a, H-4026 Debrecen, Hungary. use of radioactive standards for approximating unknown
E-mail: szaloki@tigris.klte.hu detector parameters, such as thickness of the dead layer,
† On leave: KFKI Energy Research Institute, P.O. Box 49, H-1525
active region of the crystal and absorbing layers between
Budapest, Hungary
Contract/grant sponsor: Hungarian Education Ministry;
x-ray source and detector crystal. In this respect, a simple
Contract/grant number: FKFP 0789/1997; Contract/grant number: experimental method was reported by Cohen3 to measure
FKFP 0146/1999. the different thin absorbing layers on/in the Si(Li) crystal
Contract/grant sponsor: National Committee for Technological
Development. (ice, dead layer, contact layer, etc.); it involved the applica-
Contract/grant sponsor: OTKA; Contract/grant number: T031971. tion of an extremely thin 241 Am radioactive source located

Copyright  2001 John Wiley & Sons, Ltd.

50 I. Szalóki et al.
on the surface and neglected the self-absorption effect. The
method is based on the different attenuation properties of
the lines of Np L series, i.e. comparison of the detected
intensity ratio with the original values allows the calcula-
tion of the absorber thickness. Lépy et al.4 determined the
efficiency calibration of an Si(Li) detector by using energy-
tuned synchrotron radiation in the 0.7–7.0 keV energy range
and measuring the radiation intensity with a proportional
counter. For high-energy x-ray and
-spectrometry with Ge- radiation emitted from the sample in the air between the
type detectors, the determination of the efficiency curve over
the 30–2000 keV energy range must also be available, which
requires the use of long-lived standard
-sources. An appro- the primary x-rays and  is the detector take-off angle (see
priate model for the efficiency function must describe all
the secondary physical processes (scattering, escape effects,
etc.) that occur in the Ge crystal and give a significant con-
tribution to the detector signal due to the higher energy
range of the detected x-rays and the larger crystal volume
(ca 1–100cm3 ) in comparison with Si(Li) (ca 0.2–0.3 cm3 ) or
Si-PIN detectors (ca 0.001–0.002 cm3 ). To study the influence
of these secondary effects on the detector signal is outside the
scope of recent investigations. Most of the related papers deal
with the efficiency calibration of Ge detectors using empiri-
cal equations,5,6 such as polynomial or log–log polynomial
functions of the x-ray photon energy.
THEORETICAL RELATIONSHIPS
In the energy-dispersive x-ray fluorescence (EDXRF) and
wavelength-dispersive XRF (WDXRF) techniques, the FPM
is widely used for determining the quantitative composition
of different materials based on the early work of Shiraiwa
and Fujino.7 The procedure does not require the use of
a series of standard samples and allows the analysis
of different types of materials8 in medical physics,9 in
industry10 and in environmental applications.11 An early
study (Ref. 2 and papers cited therein) dealt with the
determination of the efficiency function of semiconductor
detectors through measurement of the x-ray fluorescence
signal; however, the authors applied this technique partially
at the low x-ray energy range (E < 5 keV). The FPM
generally offers a simple mathematical description of the
relationship between the characteristic intensities and the
concentrations of sample elements. In this respect, some
initial conditions have to be assumed: (i) the sample surface
is flat and parallel to the planar-type detector surface, (ii) the
excitation and secondary x-ray beams are well collimated
and (iii) the irradiated sample is homogeneous. Under these
conditions, the following equation approaches the recorded
characteristic intensities emitted by pure-element samples7,8
ri 1 photo
Ii D Pωi µi .E/Ki exp[ dair µair .Ei /]
ri
1 exp. di Ai /
ð ε.Ei /
Ai
where
µi .E/ µi .Ei /
Ai D C
sin sin 
is the absorption factor, i D 1, 2, . . . , n, n is the number of
measured pure-element samples, Ei and Ii are the energy
Copyright  2001 John Wiley & Sons, Ltd.
and the intensity of the analysed line for the ith pure
element sample, respectively, ωi is the fluorescence yield, ri
photo
is the absorption edge jump ratio and µi .E/ and µi .E/ are
the photoelectric and the total mass absorption coefficients,
respectively, of the ith pure element sample at a photon
energy E. The parameter Ki gives the line emission fraction
in the entire K or L series, di is the thickness of the ith pure
element sample and dair is the pathlength of the secondary
sample and the Be window of the detector. The term is
the average entrance angle relative to the sample surface for
Fig. 1). The detected intensity depends on the solid angle of
the detector and the photon flux impacting on the sample
surface. During the present experiments all the geometrical
parameters which influence the detected intensity and the x-
ray flux emitted by the 125 I source in the unit solid angle
were constant and can be involved in variable P as a
proportional factor. This relationship provides a reasonable
opportunity for the calibration of the efficiency function (ε)
and the determination of critical parameters of the applied
detector.
The efficiency function of an ED semiconductor detector
(ε) can be approximated by Eqn (2) considering the depen-
dence of the transmission on the thickness of the Be window
(dBe ), the active layer (daSi ) and the inactive layer (dinSi ) of the
semiconductor crystal and the contact layer on its surface
(dcon ):
 
µBe dBe C µSi dinSi C µcon dcon
εcalc .E/ D exp
sin 
  
µSi daSi
ð 1 exp .2/
sin 
where µBe , µcon and µSi are the mass absorption coefficients
of the Be window, contact layer and silicon, respectively.
The angle , which is the same as defined in Eqn (1), is the
average entrance angle of the x-ray beam relative to the Be
window. In this case, the detector has to be considered as a
planar-type detector being parallel to the sample surface. The
.1/
Figure 1. Scheme of the geometrical arrangement of XRF
measurements for efficiency calibration of PIN and Si(Li)
detectors and application of an FPM approach.
X-Ray Spectrom. 2001; 30: 49–55

ε.E/ function can also be derived from Eqn (1) at individual
energy values:
I i Ai
εmeas .Ei / D
ri 1 photo
Pωi Ki µi .E/ exp[ dair µair .Ei /]
ri
ð [1 exp. di Ai /]
The above-mentioned unknown parameters are involved
in Eqn (2), and can be estimated by fitting the calculated
function to the εmeas (Ei ) values given in Eqn (3) by
minimization of the following chi-squared expression:
X
n
[εmeas .Ei / εcalc .Ei /]2
2 D
iD1
.n k 1/i,2 meas
where i,meas is the standard deviation of the measured
efficiency values and k is the number of fitted parameters.
The uncertainty i,meas of the εmeas .Ei / values were estimated
by error propagation analysis using Eqn (3) and taking into
consideration the error of the intensities and the published
errors of the involved basic parameters. The calculation of
the fluorescence yield, absorption jump ratio and relative
intensity were based on tabulated data of Storm and Israel12
and fitted empirical functions proposed by Poehn et al.13
Leroux and Thinh14 published a simplified equation for
calculation of the total mass absorption functions using two
parameters, p1 and p2 , in an empirical expression:
µ.Z, E/ D p1 .Z, E/Ep2 .Z,E/
where Z is the atomic number and E is the energy of the
x-ray beam. The difference between photo-mass absorption
and total mass absorption coefficients is less than 1–2% in the
energy range 1–25 keV for elements from Al to In; therefore,
the photo-mass absorption function in Eqns (1), (2) and (3)
-lines in the 50–1800 keV
can be substituted by the total mass attenuation function.
A similar model to that given in parametric Eqn (2)
was proposed by Martinez et al.15 for an HpGe detector,
supplementing Eqn (2) with an analytical expression for the
efficiency relationship describing the escape effect of photons
from the detector crystal. Their fitting procedure was based
on the comparison of measured and tabulated values of the
K˛/Kˇ ratios for thin pure samples and the results were
successfully verified by Monte Carlo simulations.
EXPERIMENTAL
In this work two Si-PIN (FWHM D 260 eV, E D 6.403 keV)16
and a conventional Si(Li) (FWHM D 185 eV at E D 6.403 keV)
detectors were studied. A brief scheme of the applied
measuring geometry can be seen in Fig. 1, illustrating the
main real geometrical conditions, which allows the use of
a simplified version of the FPM calculations. Pure element
samples from Z D 21 to 48 were irradiated with Te K˛
photons emitted by a ring-shaped 125 I radioactive source
having ¾10 MBq total activity. The primary and secondary
x-rays can be approximated as parallel beams and the planar-
type detectors were placed parallel to the sample surface.
For the intensity calculation, a flat sample surface and a
Copyright  2001 John Wiley & Sons, Ltd.
Efficiency calibration of energy-dispersive detectors 51
small excitation and detection solid angle were assumed as
shown in Fig. 1. Corresponding to the cylindrical symmetry
of the geometrical arrangement, the irradiated samples were
.3/ formed in a flat shape, with a diameter of 10 mm. To avoid
primary radiation of the 125 I radioactive source into the Si
crystal, a lead layer of 5 mm thickness was installed in the
sample–source holder between the detector and the source.
The sample was placed at 2 and 10 cm distances from the
radioactive source and the detector window, respectively.
In the case of the Si(Li) detector, additional measurements
were carried out in the low-energy range, 1.4 < E < 5 keV,
using Al, Si, S, Sc and Ti elemental samples and an 55 Fe
radioactive source, under vacuum. Nevertheless, the low-
.4/ energy excitation could not be performed with Si-PIN
detectors since their structure did not allow the mechanical
connection between the vacuum chamber and the measuring
surface of the detector.
Generally, in the efficiency calculation, the solid angle
of the impinging x-ray flux to the detector crystal must be
considered, which is difficult without an exact knowledge of
the geometrical parameters of the detector–source–sample
arrangement and the detector crystal. The measuring geom-
etry was adapted to the conditions of the simplified FPM
calculations, as discussed above. Therefore, a narrow collima-
tor, manufactured from high-purity Al (99.999 wt%), with an
inner hole of 1.5 mm diameter and a Ta pinhole, were applied
between the target and detector window. This implied that
the emergence angle () of the secondary x-rays to the Be
window was close to 90° and the detection probability of the
.5/
secondary radiation scattered on the surrounding material of
the detector was decreased. The AXIL17 program was applied
for quantitative evaluation of each x-ray spectrum operating
with a non-linear least-square minimization routine.
The calibration procedure for the HpGe detector
(¾100 cm3 ) was carried out with a set of standard long-lived
radioisotopes (Table 1) emitting
energy range. Since this type of detector has a thick Al win-
dow (¾0.75–1.25 mm), the low-energy part of the efficiency
curve (E < 50 keV) decreases drastically. The calculated
intensities were corrected with the appropriate half-life and
the coincidence effect originated by the pile-up of different
lines. The measuring set-up for the samples was constructed
as a cylindrically symmetrical geometry corresponding to the
shape of the detector crystal (except for the PIN detectors).
RESULTS
In order to search for the minimum value of the  2 function in
Eqn (4), the Optimisation Toolbox of the MATLAB software
was used. The results of the fitting for the detectors studied
are shown in Figs 2–4. They include the experimental
[Eqn (3)] and the calculated [Eqn (2)] efficiency values. In
the case of the PIN detectors, the fitted model does not
depend strongly on the thickness of the absorber layers,
i.e. dead layer .dinSi /, Be window and air pathlength, since
these parameters influence significantly the low-energy part
(E < 5 keV) of the efficiency curve. The optimum values of
the active layer were obtained as 209 and 145 µm, and the
inactive and contact layers were found to be less than 0.1 µm,
X-Ray Spectrom. 2001; 30: 49–55
52 I. Szalóki et al.

Table 1. Parameters of the radioisotopes used for empirical efficiency calibration of the HpGe18,19
detector

Energy Activity Energy Activity

Isotope (keV) (kBq) Branching Isotope (keV) (Bq) Branching
133  226 
Ba 53.2 
 2.20 Ra 768.4  4.88
 

133
Ba 81  
 32.80 226
Ra 806.2 

 1.23

 
133
Ba 160.6 

 0.72 226
Ra 934.1 


 3.16
 
133
Ba 223.1  0.47 226
Ra 609.3 

 46.10


133
Ba 276.4 
 304.3 7.29 226
Ra 665.5 

 1.56

 

133
Ba 356  
 62.30 226
Ra 839.0 

 0.59
 
133
Ba 383.9 


 8.84 226
Ra 1052.0 


 0.32
 
133
Ba 302.9 18.60 226
Ra 1120.3 

 15.00
152  226
Eu 121.8  28.40 Ra 1155.2 1.69

 
152
Eu 244.7 

 7.51 226
Ra 1238.1 


 762.37 5.92
 
152
Eu 295.9 


 0.44 226
Ra 
1281.0 
 1.47
 

152
Eu 344.3 

 26.60 226
Ra 
1408.0 
 2.48

 
152
Eu 367.8 

 0.86 226
Ra 1509.2 


 2.19

 
152
Eu 
411.1 
 2.23 226
Ra 1661.3 

 1.15
 

152
Eu 444.0 


 3.12 226
Ra 1729.6 

 3.05

 

152
Eu 488.7 
 0.41 226
Ra 1764.5 

 15.90
152 226

Eu 564.0 30.5 0.49 Ra 1847.4 2.12

152
Eu 586.3 


 0.46 54
Mn 834.8 101.8 100.00

152
Eu 778.9 

 13.00 137
Cs 661.6 31.19 85.10

 
152
Eu 
867.4  4.21 57
Co 122.1  85.60


152
Eu 964.1 


 14.60 57
Co 136.5 99.23 10.60
 
152
Eu 1005.3 
 0.65 57
Co 692.0  0.16


152
Eu 1212.9 
 1.40 60
Co 1173.2 31.44 99.90


152
Eu 1299.1 
 1.63 60
Co 1332.5 100.00
152
 241
Eu 1408.0 20.80 Am 59.5 30.72 35.90

which does not influence the shape of the fitted curve in the
high-energy region (E > 5 keV). This result allows one to
omit these parameters from the efficiency formula equation
[Eqn(2)] in the present application. It is remarkable that the
effective thickness is significantly less than that published by
the manufacturer.16
The window of the Si(Li) detector was covered addition-
ally with a polyethylene foil by fixing it with an organic glue
to protect the Be sheet and this resulted in a layer equivalent
to a Be thickness (¾36 µm) higher than the nominal value

Figure 2. Relative efficiency function for the Si-PIN detectors.

The optimum values for the thickness of the active layer were
found to be 209 and 145 µm for PIN1 and PIN2, respectively. Figure 3. Efficiency function of a Si(Li) detector in the
The individual points were calculated from measured values 1.5–26 keV energy range. The fitted values of the parameters
with Eqn (3) and fitted with Eqn (2). are summarized in Table 2.

Copyright  2001 John Wiley & Sons, Ltd. X-Ray Spectrom. 2001; 30: 49–55
 Efficiency calibration of energy-dispersive detectors 53

In order to minimize the number of fitted parameters,

different types of polynomial functions were tested (lin-
ear, linear–log, log–log, etc.). The best performance was
found when a fourth-order log–log-type polynomial func-
tion was fitted to the individually calculated efficiency
values: ( 4 )
X
i
ε.E/ D exp ai [ln.E/] .6/
iD0

The goodness of the fitting is illustrated by Fig. 4. Our further

research will be focused on establishing an appropriate
model for the description on the high-energy tendency of the
efficiency curve of HpGe, clarifying the large discrepancies
Figure 4. Full-energy relative efficiency curve of a HpGe
between experimental and calculated data.
detector (¾100 cm3 ) with fitted log–log-type polynomial.

(25 µm) given by the manufacturer. Two standard samples,
Sr and Rb oxide, were used and this required a simple modifi-
cation of Eqn (3) considering the composition for calculation
-ray spectrometry
of the absorption coefficients. The fitted physical parameters
in Table 2 are in agreement with the predicted values given
by the manufacturer.
Martinez et al.15 proposed an expression for a correc-
tion factor for the HpGe efficiency calibration describing
the escape effect, which did not make a significant con-
tribution to the efficiency value [ε.11 keV/ ³ 0.15 and
ε.50 keV/ ³ 0.02] in the energy region E > 50 keV. If the
sample–window distance is less than the sample diame-
ter, the sizes of an extended sample must be considered
for calculation of the absolute
-activity per unit volume glaze thickness is not known and it cannot be removed
in the measured sample material. For this approximation,
knowledge of the radial efficiency10 relative to the central
axis of the detector is necessary and this was determined
experimentally using point-like standard isotopes (the diam-
eter of the standards were about 2 mm), listed in Table 1.
The measured intensity values were fitted with a third-
order polynomial. For illustration, a typical radial efficiency
curve for extended samples is presented with a detailed
description in Ref. 10. The efficiency at individual energy
values can be calculated from the intensities of the
-lines lead from the glaze. The EDXRF analysis of the pottery item
of the standard radioactive sources listed in Table 1 together
with the indicated energies, source activities and branch-
ing rates.18,19 In the higher energy region (E > 50 keV),
an increasing deviation was found between the fitted and
measured values of the efficiency function described by
Eqn (2). Therefore, this model does not describe accurately
the detection processes in that energy region. This obser-
vation indicates the application of an empirical approach.
APPLICATIONS
The results of the efficiency calibration procedure presented
in this paper were applied to x-ray and
in different research fields.
XRF analysis is a non-destructive method for the
determination of the composition of materials such as
different layers on solid surfaces, e.g. glaze on terracotta
pottery items. The method was applied for the measurement
of the lead content in the glaze by evaluating the L˛
and Lˇ line-groups taking into consideration the intensity
dependence on the composition and the glaze thickness.
The calculation model was based on the FPM algorithm;
the use of standard samples is not possible because the
to be checked. The attenuation of the glaze for the Pb
L˛ and Lˇ lines is different; therefore, the characteristic
intensities are influenced not only by the composition but
also the thickness of the glaze layer. This relationship offers
a chance to calculate this parameter if the Pb content is high
(5–50 wt%),20 which also requires the use of the efficiency
function of the detector. The measurements were carried
out on historical pottery items manufactured over the last
200 years, in order to investigate the leaching effect of the
was done in a local Hungarian museum using a portable PIN
diode detector.
X-ray-emitting isotopes can be widely applied for in
situ observation and tracing of physical, chemical and/or
electrochemical processes (e.g. electrosorption phenomena)
at solid–liquid interfaces.21 The relatively high attenua-
tion of low-energy x-rays provides excellent experimental
conditions (high surface intensity to solution background

Table 2. Summary of the essential parameters of the applied semiconductor detectors

Detector Window dcon (nm) dwin (µm) din (µm) da (µm) Size

PIN1 Be — 25 — 209 ¾7 mm2

PIN2 Be — 25 — 145 ¾7 mm2
Si(Li) Be ¾26 25 C 12a ¾280 2850 ¾20 mm2
HpGe Al — ¾1000 — ¾20 cm2 ð 5 cm
a
The window of the Si(Li) detector was additionally covered with a polyethylene foil having
a thickness which is equivalent to a 12 µm Be layer.

Copyright  2001 John Wiley & Sons, Ltd. X-Ray Spectrom. 2001; 30: 49–55
54 I. Szalóki et al.
intensity ratio) for in situ studies of interfacial phenom-
ena on a solid adsorbent electrode immersed in a solution
containing species labelled with x-ray-emitting isotopes.
For instance, in a recent study21 the surface excess () of
radiolabelled Zn atoms adsorbed on a polycrystalline gold
substrate was studied. A mathematical model was elabo-
rated to describe the absolute dependence of the detected
characteristic x-ray flux on the amount of the adsorbed
Zn species labelled with 65 Zn. In this study, the so-called
in situ radiotracer ‘foil method’ was used, i.e. a thin Au
layer covered with a plastic foil acts as the working elec-
trode and the deposition of radiolabelled Zn species was
detected on it. The above experiments reveal that the ‘foil
method’ is suitable for the evaluation of the surface excess
of sorbed x-ray-emitting species (65 Zn, 51 Cr, etc.) with very
high sensitivity ( values are as low as 10 12 mol cm 2 ).
This calculation requires also an accurate determination of
the efficiency curve for the PIN detector used. The val-
ues obtained by theoretical prediction were compared with
the experimental results of Zn deposition on polycrystalline
gold, and excellent agreement between the calculated and
-spectroscopic
empirically determined absolute surface activity per unit
area was found.
Quantitative electron probe microanalysis (EPMA) for
low-Z elements (C, N, O) in aerosol and sediment particles
also needs the precise evaluation of the efficiency parameters
for the applied semiconductor ED detector. Owing to the
low attenuation length of these elements, the detector must
be without a window or have a thin polymer window
-line of 137 Cs is shown in Fig. 5 without correction to the
(d ³ 200–400 nm).22 The present calculation model was used
to fit the theoretical function to the transmission data of
the thin window provided by the manufacturer. The results
were tested by quantitative analysis of large numbers of
standard particles of (NH4 )2 SO4 , NH4 NO3 , CaCO3 , CaSO4 ,
SiO2 , Fe2 O3 , BaSO4 , KNO3 and NaCl.23 The quantitative
calculation was based on a modified version24 of a single
scattering Monte Carlo program called CASINO designed
for simulation of low-energy beam interaction generating
x-ray and electron signals.25 For handling and processing the
large amounts of measured spectral and morphological data,
an automated algorithm and computer frame program was
developed, which uses the calculated efficiency function
based on the known detector parameters. The analysis
of these different standard particles yielded data22 that
agreed well with the nominal values and this demonstrates
indirectly the reliability of this model.
The bottom sediment composition of lakes or oxbow
areas is one of the most relevant indicator of environmental
changes of biological and geochemical processes in the water
body and at the sediment–water interface. In a previous
research project sediment core samples of 700–900 cm
length were collected from a Hungarian peat bog11 and
the subdivided samples were analysed quantitatively by
Inductively coupled plasma atomic emission spectrometry
(ICP-AES) and EDXRF analysis. The measurements were
carried out using an Si(Li) detector (FWHM D 180 eV) and
Mo and Cr x-ray tubes exciting sequentially the samples,
and a new FPM calculation algorithm was developed to
determine the concentrations of elements from Al to Sr
Copyright  2001 John Wiley & Sons, Ltd.
without using standard samples. Of course, the FPM code
requires the exact knowledge of the efficiency curve, which
was determined by the above-described method, in the
energy range 1–30 keV. In order to verify an appropriate
soil development model,11 the core samples were analysed
by both ICP-AES and XRF after sequential extraction to
obtain detailed information about the origin and also the
biological, physical and chemical reasons for the mobilization
and transport of trace metals. The calibration process for the
date of the core samples along the length is a critical point
of these investigations; this was done by the radiocarbon
method. However, the accuracy of this procedure is limited
especially in time intervals in the last 10–40 years. Our recent
interest is concentrated on the oxbow area of the river Tisza,
to determine the level of the sedimentation processes and
the transport of sediment material and the related pollutant
elements, which cannot be recorded by this technique
with the quantitative analysis of layers from 200–400 cm
depth. These depth values were measured relative to the
actual water level. To improve the reliability and to extend
the capability of the dating procedure,
measurements on the natural radioactivity of 210 Pb and 137 Cs
radioisotopes were carried out. The significantly higher 137 Cs
activity level can be associated exactly with the Chernobyl
disaster (1986) and the explosions of atomic bombs in
the 1950–1960s. This higher activity, above the normal
background level, of this isotope indicates the date of that
sedimentation layer. A typical distribution of the 661 keV
half-life of this isotope. Two significant ‘peaks’ on the activity
curve can be clearly observed, indicating the dates of those
layers as 1986 and 1954–59. The first signal decreases exactly
at 270–275 cm depth, which can be dated to the middle
of the 1960s, when the experimental explosions of nuclear
bombs were limited. The migration in the vertical direction
and the delayed deposition of the 137 Cs isotope should cause
the widening of these two ‘peaks,’ which is influenced by
the composition of the surrounding soil, deposition rate
Figure 5. Distribution of the 137 Cs intensity (E D 661 keV
line) versus depth relative to the current water level. The first
‘peak’ around 230–244 cm is associated with the Chernobyl
disaster, which occurred in 1986, and the second one around
274–280 cm originates from the series of nuclear bomb
explosions during the ‘cold war’ period (1954–59). The average
deposition rate on the water bottom is ¾1.4–1.9 cm per year
depending on the flooding events and weather conditions.
X-Ray Spectrom. 2001; 30: 49–55

and flooding events of the Tisza river. The detailed model
for these processes and the latest results will be published
elsewhere.
CONCLUSION
A simple analytical expression was used to model the
full-peak relative efficiency function of three different
semiconductor x-ray detectors in the energy range 1 <
E < 35 keV; it provided good agreement between measured
and calculated efficiency values. The procedure was based
on the FPM calculations approximating theoretically the
characteristic intensities of pure elements. The excitation
was carried out with radioactive sources (55 Fe, 125 I). For
detection of high-energy x-rays (E > 35 keV), Ge-type
detectors have to be applied. The best efficiency calibration
procedure was found when the individually calculated
efficiency values were fitted with an empirical equation:
fourth-order log–log–type polynomial function. The present
procedure offers an excellent opportunity to determine
the essential Si-type detector parameters using technically
similar measurements needed for the application of FPM
based on XRF analysis of pure samples or chemical
compounds with known compositions. Therefore, it can
be built into any automatically performed XRF or EPMA
routine for quantitative analysis since it needs only a few
characteristic intensities of standard samples which are also
necessary for the application of FPM-based concentration
calculations. The general procedure was tested in different
fields of XRF analysis and its unique application was
presented by in situ radiotracer studies of Zn electrosorption
on a polycrystalline gold electrode.
Acknowledgements
This work was supported by the Hungarian Education Ministry
under contracts FKFP 0789/1997 and 0146/1999, the National
Committee for Technological Development and OTKA under
contract T031971.
Copyright  2001 John Wiley & Sons, Ltd.
Efficiency calibration of energy-dispersive detectors 55
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