DK1838 - ch03 Chapter 3 (Three) Handbook of X Ray Spectrometry

3
Energy-Dispersive X-ray Fluorescence

Analysis Using X-ray Tube Excitation
Andrew T. Ellis
Oxford Instruments Analytical Ltd., High Wycombe, Buckinghamshire, England
I. INTRODUCTION
The scope of this chapter is laboratory and industrial x-ray uorescence (XRF) analysis
systems in which x-ray tubes are used for excitation and energy-dispersive (ED) semi-
conductor detectors, as opposed to Bragg-diraction (wavelength) dispersion devices,
are used. Such ED detectors directly measure the energy of the x-rays by collecting the
ionization produced in a suitable semiconductor material. The coverage of this chapter
specically excludes the following topics, which are covered in other chapters: on-line
EDXRF systems (see Chapter 7), total-reection XRF (TXRF) (see Chapter 9), polarized
beam XRF (see Chapter 10), and x-ray microuorescence (XRMF) (see Chapter 11).
Early approaches to EDXRF used gas proportional counters or scintillation de-
tectors to determine directly the energy of the x-rays. Such systems were limited in their
application because of the inherently poor energy resolution, which precluded the se-
paration of characteristic x-rays of adjacent elements in the periodic table. The limited
actual energy resolution of such detectors led them to be known as nondispersive, but this
drawback has been eectively countered in some benchtop instruments through the use of
novel arrangements of primary and secondary beam lters (Ross, 1928; Kirkpatrick, 1939;
Kirkpatrick, 1944; Field, 1993). The real breakthrough in EDXRF came in the late 1960s
(Bertolini et al., 1965; Bowman et al., 1966; Elad and Nakamura, 1966; Aitken, 1968) with
the arrival of solid-state semiconductor diode detectors and their associated pulse pro-
cessing circuits. These detection systems were developed through the early 1970s, often in
electron microscopes, to the point at which practical x-ray spectrometry with an energy
resolution of 200 eV or less became possible (Frankel and Aitken, 1970; Landis et al.,
1971; Heath, 1972). Although the energy-resolution capability of semiconductor detectors
remained greatly inferior to that achieved by wavelength-dispersive (WD) XRF systems,
the increased eciency inherent in the energy-dispersive method compensated in many
analytical applications and permitted the use of a multiplicity of experimental geometries
not practical with WDXRF. A wide variety of EDXRF analytical systems based on
radioisotopoe sources, x-ray tubes, charged-particle accelerators, microprobe electron
beams, and synchrotron light sources have been developed in recent years.
Copyright 2002 Marcel Dekker, Inc.

Within the scope of this chapter, only EDXRF systems in which x-ray tubes are used
for excitation will be considered further. The material in this chapter discusses the in-
strumental aspects of the energy-dispersive method, with particular emphasis on the use of
low-power, compact x-ray tubes in combination with semiconductor detectors.
The basic components of an EDXRF instrument within the scope of this chapter are
depicted schematically in Figure 1. Each of the main subsystems of such an instrument is
covered in detail in the following sections.
II. X-RAY TUBE EXCITATION SYSTEMS
In EDXRF spectrometry, there is no physical discrimination of the secondary radiation

that leaves the sample and enters the detector. This means that all photons of all energies
in this secondary beam interact with the detector. The detector and its associated signal
processing chain have a limited capacity to process these events and this is typically in the
range 150 kcps. As a direct consequence, EDXRF has a limited total counting capacity
Figure 1 Basic components of a tube-excited EDXRF instrument.

for all element x-ray emissions and it is, therefore, essential that the content of the incident
spectrum be optimized for its useful information. This may require that more than one
acquisition be made under dierent excitation conditions in order to control the range of
energies needing to be collected in the detection system. Alternatively, the excitation
system may be optimized to increase the intrinsic peak-to-background ratio through the
use of alternative geometries such as TXRF or polarization EDXRF. In both these cases,
however, higher-power x-ray tubes are typically required and there is still the need to apply
some type of selectivity to the excitation system. This selectivity can be achieved in TXRF
using more than one tube target materialtypically Mo and W. In the case of polarization
EDXRF, more than one tube high voltage or polarizing element is likely to be applied.
This selectivity of excitation employed in EDXRF is completely the reverse of
conventional WDXRF practice. In WDXRF, the high discrimination power of the dis-
persion and detection process and its associated losses coupled with very simple detection
and counting systems allow very high count rates to be processed for each narrow wa-
velength band. Thus, the detection process is highly selective and the count rates in an
individual element channel with a modern WDXRF system can be well in excess of 106
CPS. Typically, the simple rule of thumb in WDXRF would be to use twice to three times
the kilovoltage (kV) of the absorption edge of the highest element of interest and then to
apply the maximum allowed current at that setting. In summary, we may regard the es-
sential operational dierence between EDXRF and WDXRF spectrometry as follows:
WDXRF uses broad-band excitation and selective detection.
EDXRF uses selective excitation and broad-band detection.
There are various ways in which selective excitation is achieved in EDXRF spec-
trometry. The use of TXRF and polarization is covered elsewhere in this volume and will
not be considered further here. The most important modes in which selective excitation is
realized in EDXRF are as follows:
Selection of tube anode material
Variation of tube voltage (kV)
Use of primary beam lters
Use of secondary targets (and associated lters)
The selection of tube anode material is typically a once-o decision made at the time of
purchase in view of the intended application. The high purchase cost of x-ray tubes
generally precludes operational changes and low-power dual or multiple (Kis-Varga, 1988)
anode x-ray tubes are not commercially available.
The types of x-ray excitation arrangements are shown schematically in Figure 2.
The following subsections describe typical arrangements for excitation and describe
how optimum excitation conditions can be determined. Earlier work on this subject may
be found in the XRF literature (Sandborg and Shen, 1984; Vane and Stewart, 1980;
Gedcke et al., 1977).
A. Direct and Filtered Direct Excitation

In Figure 2, the beam (1) represents the conguration used for direct excitation of the sample
by the x-rays emitted from the anode. A primary x-ray beam lter can be used to modify the
spectrum from the x-ray tube that is nally used to excite the elements in the sample.
The optimum selection of kV and primary beam lter are critically important for
obtaining the best data from an EDXRF system. As with all spectrometry methods, the
Figure 2 An x-ray tube and typical excitation geometries. The high-energy electron beam strikes
the anode to produce x-rays. (1) Direct or direct filtered: the flux (1) is used directly to strike sample
(1) or is first passed through a primary beam x-ray filter. (2) Secondary target: the primary flux (1)
strikes a secondary target 2, which generates a flux of x-rays (2), which strikes the sample at 2.
(3) Transmission geometry: the beam (3) is directed through the anode to the sample.
principal driver for best precision and detection limits is peak-to-background (P/B) ratio.
However, as mentioned earlier, the limited total counting capacity of the EDXRF system
and the analysis of multielement samples are added complications in deriving optimum
excitation conditions. In general, the kV governs the sensitivity and the primary beam
lter governs the background.
The energy distribution of the spectrum arriving at the sample governs the eec-
tiveness of excitation for element XRF lines. In order to excite x-ray uorescence, it is
necessary to have incident x-ray energies above the absorption edge for the elements line
series to be excited. In order to have adequate excitation, there needs to be a high intensity
of x-rays with energies higher than the edge and conventional wisdom has suggested that
the tube kV should be 1.52 times the absorption edge of interest. This overvoltage en-
sures that there is a substantial proportion of the x-ray tube output spectrum available for
excitation of the element line(s) of interest. Figure 3 shows the unltered x-ray tube
spectrum scattered from a thin-polymer-lm sample when the x-ray tube is operated at
5, 10, and 15 kV. The observed scatter spectrum is a reasonable representation of the
spectrum striking the sample and clearly shows the following:
Figure 3 Scattered, unfiltered excitation spectrum provided by a silver target x-ray tube operated
at (1) 5, (2) 10, and (3) 15 kV.
The high-energy cuto at the operating kV. This is also known as the DuaneHunt
limit.
The bremsstrahlung hump.
The intense characteristic AgL lines (around 3 keV) from the tube anode. The intensity
of the AgL lines increases with the kV (i.e., as the overpotential increases).
The tube L lines of Ag and Rh are particularly eective for exciting the light elements in
the range 12.5 keV. Once higher-energy lines (e.g., FeK at 6.4 keV) are sought, the L
lines provide no excitation, as they are lower in energy than the absorption edge (FeK at
7.11 keV) and the bremsstrahlung hump provides the excitation. Despite the highest in-
tensity of the bremsstrahlung being lower than AgL lines, it is the integrated excitation
spectrum, higher in energy than the absorption edge, which is important. When the x-ray
tube kV exceeds the energy of the K edge of the tube anode material, the characteristic K
lines will begin to dominate the excitation spectrum. This is shown in Figure 6, which
depicts the scattered excitation spectrum with the tube operated at 35 kV, at which the
AgK characteristic lines are strongly excited.
The basic sensitivity for analysis is governed by the kV applied to the x-ray tube and
an example of this is seen in Figure 4. The sample was a pressed pellet and the kV was set
in the range 616 kV using a vacuum path in the spectrometer and no primary beam lter.
At each kV, the rhodium-target x-ray tube current was adjusted to give 50% deadtime.
The K-series line intensities were used and the sensitivity for each element has been nor-
malized to the value at 10 kV. From the plots, the following are clear:
The Si intensity falls o as the kV increases. This is due to the increasing distance of
the tube main spectrum from the SiK absorption edge and to the increased relative
contribution of the other elements to the total counts in the spectrum. This latter
Figure 4 Effect of kV on sensitivity for the major elements in a geological sample (see text for
details).
factor is important and derives from the limited total count rate for the whole
spectrum.
The FeK lines are not excited until at least 8 kV is applied. The FeK absorption edge
is at 7.111 keV and the maximum sensitivity for Fe is at approximately twice this
value.
The general rule of thumb in which the kV is set to twice the highest absorption-edge
energy is a reasonable place to start. However, as more elements are sought across a wider
energy range, there usually comes a point at which the balance of the spectrum is un-
favorable for the analytical problem being solved. When this happens, split the spectrum
into two or more areas of interest and apply a kV to best suit each of these element ranges.
In any event, as the kV and the number of elements increase, the importance of using a
primary beam lter and splitting the spectrum into optimized energy regions increases.
B. Primary Beam Filter Selection

A primary beam lter acts as an x-ray absorber and it is placed between the x-ray tube and
the sample to modify the x-ray tube output spectrum to which the sample is exposed. In
general, the kV is selected rst to ensure high excitation sensitivity and then an appropriate
lter is chosen. The lter acts to reduce scattered background in the region of interest and
to reduce the excited intensity of lower-energy peaks. The characteristics of the lter are
dened by its x-ray absorption curve, which is controlled by selecting the material and its
thickness. Filters are typical thin, pure metal foils of thickness in the range 10500 mm.
Some typical lters, the range of kV used with each, and the applicable optimum element
range (K lines) are shown in Table 1.
The x-ray tube spectrum provided by unltered radiation can be seen in Figure 3.
The eect on the x-ray tube spectrum of applying a thin and thick aluminum lter is seen
in Figure 5, where a tube voltage of 15 kV is used.
The aluminum acts as a simple absorption lter, having a single absorption edge at
1.56 keV. From the plots, it is clear that the aluminum lters both completely absorb the
AgL lines as a consequence of the high-mass-absorption coecient of around 700 cm2=g.
The hump at lower energy provided by the spectrum ltered though thin Al yields good
P=B ratios for elements in the S to V range (2.35 keV). The absence of the AgL (or RhL,
MoL) lines from the tube removes their spectral interference and avoids the need for these
x-rays to consume counting capacity. The thick aluminum lter pinches the low-energy
side of the bremsstrahlung hump, providing high P=B ratios for the elements with lines in
the range 38 keV.
The combination of kV and an absorption lter provides an energy region in which
the P=B ratio is optimal. On the low-energy side of this region, the excitation is suppressed,
which allows more of the systems counting capacity to be used in the region itself. On the
high-energy side of the region, the excitation from the tube is tuned to provide a high
integrated intensity above the energy of the absorption edges of the element lines of in-
terest. The use of a thick copper lter with maximum kV is another example of this type of
lter. The copper lter used is generally thick enough to completely absorb the x-ray tube
anode K lines, which are of high energy (AgKa is 22.1 keV). Such an arrangement provides
for the eective determination of Ag and Cd using a silver anode x-ray tube. At the other
end of the energy scale, a cellulose lter is a weakly absorbing lter which suppresses the
AgL lines.
The so-called Regenerative Monochromatizing Filter (RMF) is a particularly im-
portant lter in tube-excited EDXRF spectrometry. The lter acts on the x-ray tube anode
K lines so the kV must be suciently high above the K absorption edge of the
anode material to generate intense K characteristic emission. The same element as the
anode material is used to preferentially transmit the characteristic K x-rays generated in
the anode. The lter takes its benet from the fact that an element has a low-mass-
Table 1 Typical Primary Beam Filters and Their Range of Use
Filter Thickness kV range Elements Comments
No filter N=A 450 All, NaCa Optimum for light elements

with 48 kV excitationa
Cellulose Single sheet 510 SiTi Suppresses tube L linesa
Thin aluminum 2575 mm 812 SV Removes tube L linesa
Thick aluminum 75200 mm 1020 CaCu Good for transition element
metal alloys
Thin anode element 2575 mm 2540 CaMo RMFb, wide range and good
trace analysis
Thick anode element 100150 mm 4050 CuMo RMFb, good for trace analysis
of heavy-element L lines.
Copper 200500 mm 50 >Fe Suppresses tube K lines
a
Needs to be used in conjunction with vacuum or He path to remove the air in the spectrometer that would
severely attenuate the low-energy lines and result in ArK lines in the detected spectrum.
b
Regenerative monochromatizing lter (RMF). The same element as the anode material is used as the lter
material to preferentially transmit the characteristic K x-rays generated in the anode.

Figure 5 Scattered excitation spectrum provided by a silver target x-ray tube operated at 15 kV.
The plots show the effect of two thicknesses of an Al primary beam filter: (1) unfiltered; (2) thin Al
filter; (3) thick Al filter.
absorption coecient for its own characteristic lines, as these lie immediately below the
absorption-edge jump. In the case of Ag, the AgKa1,2 lines are at 22.1 keV and the
absorption coecient of Ag for this energy is only 14 cm2=g.
The eect of two silver primary lters, of dierent thickness, on the spectrum from a
silver anode x-ray tube operated at 35 kV is shown in Figure 6. The unltered 35-kV
excitation (curve 1) provides equally intense AgL and AgK characteristic lines and a broad
bremsstrahlung hump centered on 1215 keV. Any element in the 515 keV range will
have the benet of excitation by both the AgK characteristic lines and the bremsstrahlung.
However, there exists the disadvantage of sitting on scattered background derived from
the radiation in the bremsstrahlung hump. With the thin Ag lter in place (curve 2), the
AgL characteristic lines are completely absorbed and the bremsstrahlung hump is reduced
to a low-energy tail on the AgK characteristic lines. The resulting excitation yields high
P=B ratios for lines in the energy range 412 keV. Use of the thicker Ag lter (curve 3),
reduces even further the residual bremsstrahlung below the AgK lines and provides
pseudomonochromatic radiation, which yields high P=B ratios for lines in the energy range
515 keV. The strongly ltered AgK line excitation provides excellent sensitivity and
background reduction and a clear, intense Compton-scatter peak, which is good for trace
analysis where a matrix correction based on Compton scatter is used. The same can be said
for anode and lter materials of Mo, Rh, and Pd, which also provide characteristic K lines
in this important region of the spectrum.
A specic and well-documented example of optimum selection of x-ray tube anode,
excitation kV, and primary beam lter can be seen in work by Potts et al. (1986). In that
work, a Co anode x-ray tube and an iron primary beam lter were used to remove the
Figure 6 Scattered excitation spectrum provided by a silver target x-ray tube operated at 35 kV.
The plots show the effect of two thicknesses of Ag primary beam filter: (1) unfiltered; (2) thin Ag
filter; (3) thick Ag filter.
CoKb line which would otherwise strongly excite the Fe that typically dominates this part
of the spectrum in geological analysis.
Most modern EDXRF systems provide the ability to use more than one set of
conditions per analysis. Depending on the analytical needs, the kV and lter are chosen to
optimize the important parts of the spectrum and the data from spectra at each of these
conditions are consolidated to provide the best P=B values. In order to establish the op-
timum conditions and make the best use of analysis time, the best strategy is to select a
typical sample and then to make measurements with the dierent conditions available. Use
criteria such as detection limits to decide upon the optimum conditions for the required
analysis problem. Often, the instrument manufacturers recommendations can con-
veniently be taken as the starting point for any investigation.
C. Secondary Target Excitation

The basic geometry of secondary target excitation is shown in Figure 2. Use of this mode
of excitation for EDXRF spectrometry was rst described by Jaklevic et al. (1972), who
incorporated the secondary target inside a small, low-power x-ray tube. The high P=B
ratios that they reported were encouraging and Porter (1973) subsequently described the
rst work in which the secondary target was external to the x-ray tube. The primary ra-
diation from the x-ray tube strikes the secondary target, which then emits characteristic
radiation and generates some scattered bremsstrahlung radiation. The emitted
radiation is pseudomonochromatic and the degree of monochromaticity is further
enhanced, as in the case of the RMF in direct excitation, with a lter between the
secondary target and the sample. Filters are of the same material as the target and are
typically only used with the higher-Z targets (e.g., Mo, Ag, and Gd). With increasing
distance below the exciting lines, the absence of bremsstrahlung lower in energy than the
exciting lines results in a very rapid reduction in sensitivity. The provision of a number of
secondary targets with associated lters, which can usually be selected automatically,
provides a range of discrete and narrow excitation bands. This arrangement can be con-
veniently thought of as providing the equivalent of a number of transmission target x-ray
tubes, each with dierent anode materials. In order to generate intense characteristic ra-
diation from the secondary target, the tube kV should be two to three times the K ab-
sorption-edge energy of the element from which the secondary target is made. The K lines
are used, as they oer the highest uorescence yield, which means that there are lower
losses than with other line series. Typical secondary targets are, in decreasing energy order
of K line emission: Gd, Sn, Ag, Mo, Ge, Cu, Fe, Ti, and Al. The optimization of x-ray tube
kV, secondary target, and lter was described by Spatz and Lieser (1979).
The uorescence yield decreases as the target atomic number decreases and the ef-
ciency of x-ray production falls o rapidly below Ti. The result of this is that the lighter
elements Si to K are not well excited by secondary targets and there are few suitable
elements available to provide targets with K lines in this important region. One approach
is to use a reduced kV and a scattering target which scatters the x-ray tube L lines and
bremsstrahlung, which, as was seen for direct excitation, is eective in this energy region.
A stable polymer block provides a suitable target for this arrangement, although the
overall eciency is much lower than with direct excitation. There are two other ar-
rangements that eliminate this limitation. The rst is to use a second x-ray tube whose
geometry provides for direct, and perhaps direct ltered excitation. Such an arrangement
adds considerable cost and complexity but does oer optimum performance. It is possible
for both tubes to be run from the same high-voltage power supply. The second approach is
to provide mechanical repositioning of the x-ray tube such that it can be operated either in
secondary target or in direct and direct ltered mode. The positional repeatability of the
mechanical arrangement needs to be excellent if this approach is adopted. The mechanical
complexity, which inevitably adds cost and some possibility for unreliability, has not
stopped this approach from being used in the past with some success in one commercially
available instrument. One disadvantage of this approach is the time that is needed for the
mechanical switching, which can be a severe penalty if a number of acquisitions are re-
quired for a complete analysiswhich is usually the case. Very recently, a so-called Wide
Angle Geometry was described by Yokhin (2000), in which a single, xed x-ray tube was
used to deliver direct unltered or ltered and secondary target excitation. This ar-
rangement was made possible using the wide cone x-ray beam from the special x-ray tube
and a proprietary x-ray beam distributor.
The reduction in overall excitation eciency when using secondary targets is usually
oset by increasing the x-ray tube power available. A tube providing close geometric
coupling and power in the range 100400 W is typically used to oset the low overall
eciency of excitation. In order to eciently excite the GdK lines, it is preferable to use an
x-ray tube capable of being operated at 60 kV. A high-Z anode such as tungsten or gold
provides the highest bremsstrahlung intensity and, therefore, the best excitation eciency
for the higher-Z secondary targets.
The high degree of monochromatization in ltered secondary target systems pro-
vides for very high P=B ratios for elements with absorption edges immediately below the
target x-ray emission lines. The background in secondary target geometry can be further
reduced using 3-axis or Cartesian geometry as described by Standzenieks and Selin (1979),
Christensen et al. (1980), and Bisgard et al. (1981).
Despite secondary target excitation gaining wide acceptance through the early 1980s,
the use of direct and direct ltered excitation has remained as the most common excitation
arrangement. This is, perhaps, partly due to the restricted energy range oered by each
secondary target+lter combination and the general need for unltered direct excitation
to obtain the highest sensitivity for the light elements. In the 1990s, the use of polarized
EDXRF (see Chapter 10) tends to have supplanted secondary target EDXRF for the
provision of high P=B ratios in some applications. In addition, improved detection systems
have continued to improve the performance of instruments using direct ltered excitation.
An application in which secondary target systems have a valuable advantage is when the
secondary target lines are selected to be just below the absorption edge of a major element,
but just above the absorption edges of trace elements. One example of this is the use of a
copper secondary target for the determination of low levels of Mn and Fe in Cu alloys. In
this example, the CuK lines from the target do not excite the Cu but are highly eective for
exciting Fe. The detection and counting system is not dominated by CuK lines, neither is
the FeKa peak interfered with by the Si escape peak from CuKa. Such applications are
few in number and, in the case of the metals industry, analysts may often prefer to use
WDXRF spectrometers.
D. X-ray Tubes
X-rays were rst discovered over a century ago (see Michette and Pfauntsch, 1996) by
Rontgen (1896a, 1896b), and since that time, they have become used in a great variety of
applications. These applications encompass medical and dental x-ray radiology and
imaging, industrial and baggage inspection, industrial nondestructive testing (NDT),
industrial thickness gauging, and x-ray spectrometry in all its guises. In most, if not all,
of these elds, the convenience of the high-voltage x-ray tube has substantial benets in
terms of convenience, safety, and availability of appropriate spectral and intensity output.
The modern x-ray tube used for EDXRF analysis is based on a design introduced by
Coolidge as long ago as 1913 (Coolidge, 1913). The basic design of x-ray tubes typically
used in EDXRF instrumentation consists of the following:
A radiation-shielded glass envelope
An independent tungsten lament with current control unit
A high-melting-point metallic anode
A high-voltage connection to the anode
A beryllium foil exit window
Some means of dissipating the heat generated
In order to operate, the x-ray tube requires a controllable, stable high-voltage power
supply capable of providing typically 560 kV. In addition, there is a low-voltage power
supply for providing current to heat the lament, thereby controlling the electron beam
current and output intensity. X-ray tubes used for EDXRF analysis are typically operated
with a power in the range of 1400 W. For direct excitation, the power output is typically,
no greater than 50 W. Reproducibility of analytical results is achieved for x-ray tube ex-
citation by operating for a measured amount of time at a xed emission current (dc op-
eration). This approach depends on the reasonable assumption that the total output x-ray
ux is proportional to the number of electrons striking the anode.
In some types of x-ray tube, a control grid can be used to modulate or pulse the
emission current. This can be used to modulate the electron beam current to ensure
constant output of radiation from the tube in dc operation or it can be used to rapidly
switch the electron beam on and o for pulsed operation. If the pulsing is synchronized
with x-ray detection, increased output countrate can be achieved by reducing pulse pileup
(see Sec. IV.C).
The key features of the x-ray tube used in EDXRF instruments are as follows:
Easily shielded and safe to operate
Compact and able to be placed close to the sample
Stable output over an extended period, typically months
Well-dened spectral output
High-voltage controllable in small increments, typically 1 kV, throughout the
operating range (typically 550 kV)
Beam current controllable in small increments, typically 10 mA, throughout the
operating range (typically 101000 mA).
The geometry and designs typically used and the characteristics of each are described in
the following sections. Further reading on the subject can be found in Skillicorn (1982,
1983).
1. Side-Window Geometry
Side-window geometry is the oldest and, perhaps, the most common x-ray tube geometry
used in EDXRF instruments and it is suitable for both high-kV and high-power operation.
Figure 7 shows the essential details of this design.
The geometric coupling of tube anode spot to sample is limited rst by the distance
of the spot itself from the exit window and then, potentially, by the tube encapsulation
itself. Typically, these tubes are operated in the range 550 kV. They can dissipate 50 W
with the need only for forced-air cooling in order to keep the tube external body below a
temperature of, say, 55 C. It is important not to exceed the maximum temperature stated
by the x-ray tube manufacturer. Higher powers (up to 100 W or 120 W) normally need
some form of liquid cooling, which is typically achieved through the use of a closed-cycle
liquid heat exchanger.
The energy spectrum that is output from a side-window x-ray tube is governed by the
tube anode material, the angle of the anode, the kV applied to it, and the exit windows
material and thickness. Tube anode materials are usually Rh, Ag, or W, although Ti, Cr,
Co, Cu, Mo, Pd, or Au is also available. The selection of anode material depends on the
intended application, but Rh, Ag, and Pd are generally the most popular, as they are
highly compatible with tube manufacture and operation. In addition, their K and L
characteristic emission lines are in regions of the energy spectrum where they oer high
sensitivity with minimum spectral interference. Dual-target x-ray tubes have been used in
attempts to maximize exibility and performance. These eorts have met with limited
success in EDXRF, in part due to the spectral cross-contamination that is typically
experienced in the designs used to date. There has been, however, considerable success in
the use of dual-target x-ray tubes for WDXRF, where the problems of spectral con-
tamination have much less impact. Typically, the anode is cut at an angle of 20 35 from
normal to the incident electron beam and the exit window is usually made from beryllium
foil of thickness in the range 50250 mm.
The tube output spectrum can be measured or estimated and such information is
important in analytical correction procedures, particularly those using fundamental
parameter calculations for which accurate and computationally convenient tube output
spectrum models are required (see Chapter 2, Sec. I.B for further details.)
Figure 7 Side-window x-ray tube.

It should be remembered that the tube output spectrum, especially with higher-
power tubes, may change with time. One way in which this can occur is through deposition
of a thin tungsten lm on the inside of the tube output window through evaporation of
tungsten from the hot lament. Such deposition is unlikely to aect the low-power tubes
typically used in EDXRF systems and, in any event, is usually taken care of through the
normal restandardization process.
2. End-Window Geometry
The design features of such an x-ray tube are shown in Figure 8. The same factors of
operation and tube spectrum apply to this type of tube as was applied to side-window
tubes. The tube spectrum is altered by the fact that the takeo angle is normal to the anode
surface and so there is minimal self-absorption by the target material. This high takeo
angle makes such a design particularly good for low-energy excitation. One of the im-
portant benets of the end-window design is the very tight coupling of anode spot to
sample that can be achieved with a sharp-nose design. The spot-to window coupling can
be close with suitable electron optics (e.g., 12 mm in the Varian EG50 design). The use of a
high positive voltage on the target minimizes the eect which repelled electrons would
have of causing an unacceptable amount of exit-window heating. This reduced heating
allows thinner beryllium windows to be used, which further improves the low-energy
x-ray output.
3. TransmissionTarget Geometry
The design features of such an x-ray tube are shown in Figure 9. In this type of x-ray tube,
the geometry is basically end window, but in this embodiment, there is a metal foil target
parallel to and inside the beryllium exit window. The incident high-voltage electron beam
Figure 8 End-window x-ray tube.

Figure 9 Schematic of a transmission target x-ray tube.
strikes and enters one side of the thin-lm target and the resulting radiation is heavily
ltered as it passes through the foil and exits the far side of the target. This novel design
was initially developed (Jaklevic et al., 1972) in order to reduce the bremsstrahlung from
the x-ray tube, which would then reduce the scattered background in the spectrum and
thereby improve detection limits. The initial design used a molybdenum transmission
target of 0.12 mm thickness and, when operated at 42 kV and up to 25 W, was shown to
give an output spectrum consisting principally of characteristic MoK radiation. The
output spectrum was comparable to an 125I radioisotope source coupled to a molyb-
denum-foil secondary target.
This type of x-ray tube was made commercially available by WatkinsJohnson
(Hershyn, 1975a, 1975b). The spectrum output from this type of tube was investigated by
Zulliger and Stewart (1975), who calculated and measured spectra from Cr, Mo, and W
transmission target x-ray tubes. The targets were either thin (50 mm) metal foils or thin
lms (510 mm) on a beryllium substrate of 0.250.5 mm thickness. The thin targets mean
that only low-power tubes (< 100 W typically) can be made successfully. These authors
found, as predicted, a substantial reduction in bremsstrahlung compared to the char-
acteristic lines and quoted detection limits for a number of applications. The Cr target was
found, not unsurprisingly, to be best for the light elements S and Ca. Although the energy
range covered was claimed to be wide, the intrinsic xed ltration of this design makes it a
less valuable general excitation source compared to a side- or end-window tube with an
external, selectable lter. A novel, multiple-target transmission tube has even been de-
scribed (Kis-Varga, 1988) in which the ve anode materials (Fe, Cu, Ge, Mo, and Ag) were
changed by a magnetic mechanism.
The intrinsic ltration of the low-energy bremsstrahlung makes this type of tube
much less suitable for excitation of low energy (i.e., < 2-keV) x-ray lines. Consequently,
their usage is limited to specic applications where the intrinsic ltration and potential for
close geometric coupling of the tube anode spot to the sample are major benets. In fact,
in one design, the WatkinsJohnson tubes did not have a target closely coupled to the
exit window, which, when combined with the intrinsic lossess in the target, led to low
output ux from the tubes and, consequently, reduced sensitivity. Finally, these tubes are
not useful when operated at low voltages (Skillicorn, 1982) due to strong absorption in the
target. This makes them much less sensitive than solid-target, side- or end-window tubes
for selectively exciting the light elements in the presence of large amounts of heavier
elements.
III. SEMICONDUCTOR DETECTORS
In this type of detector, the total ionization produced by each x-ray photon striking the
detector is converted to a voltage signal with amplitude proportional to the incident en-
ergy. Specially designed preamplication and processing electronics are employed to
maintain the linearity of the voltage signal with respect to the original charge pulse.
A multichannel analyzer accumulates an energy spectrum of the sequential events in a
histogram memory. Because the energy analysis does not depend in any way on the dif-
fraction or focusing of the x-rays by the detector, the geometry of the system is relatively
insensitive to the placement of the detector with respect to the sample. An exception to this
is in polarized excitation XRF (Chapter 10), where the orientation angle can be used to
suppress scattered background. This insensitivity to geometry and ability to place the
detector element close to the sample provides for a large solid angle and high geometric
eciency. In addition, the mechanism by which the ionization signal is measured is not
restricted to a narrow energy region, thus allowing the simultaneous detection of x-rays
over a wide dynamic range of the emission spectrum. The principal advantages of EDXRF
derive from its capability for simultaneous detection, with high geometric eciency, of
characteristic x-rays from multiple elements.
A. Fabrication and Operating Principle

The energy-dispersive detecting element is based on the simple, semiconductor diode
structure shown in Figure 10. The example shown is a structure typical for lithium-drifted
silicon, Si(Li), detectors, although the basic elements are similar for high-purity
germanium (HPGe) and other semiconductor detectors. The device is fabricated on a
cylindrical wafer of high-quality semiconductor material with rectifying p or n contacts on
opposing end surfaces. The bulk of the material is characterized by a very low con-
centration of free-charge carriers. This reduced free-carrier concentration is achieved
either with the use of extremely pure material, in the case of HPGe detectors, or through
the charge compensation of p-type silicon with lithium donor atoms in the case of Si(Li)
detectors. A typical dimension for such a detector crystal is 1080 mm2 active area with a
thickness of 35 mm.
In the geometry shown in Figure 10, the lithium-diused region acts as an n contact
and the metal surface barrier (typically an evaporated Au layer) serves as the p rectifying
contact. When the diode is reverse-biased, any remaining free carriers are swept out of the
bulk by the applied eld and an active depletion region is created. In this condition,
the only current that ows between electrodes on the respective contacts at each end of the
diode cylinder is due to thermally generated charge carriers, which are excited above the
narrow band gap of the semiconducting material. In order to minimize the noise from
these thermally generated charges, the detector crystal is operated at reduced temperature,
which is typically achieved using cryogenic cooling by means of a Dewar vacuum ask
lled with liquid nitrogen. Other cooling strategies can be adopted (see Sec. III.C).
When an x-ray photon is incident upon the active volume (i.e., depletion region) of
the diode, it normally interacts by photoelectric absorption to create an inner-shell va-
cancy in the semiconductor material together with an energetic photoelectron.
This photoelectron interacts with the atoms in the semiconductor crystal lattice to produce
multiple low-energy ionization events. This process continues until the electron comes to
rest at the end of a total range, which is short compared with the dimensions of the crystal.
The energy associated with the inner-shell vacancy is also absorbed in the crystal, in most
Figure 10 Cross section of a typical Si(Li) detector showing electrode contacts and active volume.
cases following the emission of Auger electrons or multiple low-energy x-rays and sub-
sequent re-absorption. The result of these multiple ionization process is the essentially
instantaneous production of a large number of free electronhole pairs in the sensitive
volume of the detector structure. These free-charge carriers form as a cloud from which
they are separated by the eld gradient. The front detector electrical contact, being biased
at 500 V, for example, attracts the hole and repels the electrons, the latter negative
charge cloud is swept to the rear contact and converted, by means of the FET, to an
amplied voltage pulse. The number of charge carriers produced is directly proportional
to the energy of the x-ray photon incident on the detector. Thus, the number of charges
collected results in a voltage pulse whose magnitude is, in turn, directly proportional to the
energy of the detected photon.
B. Crystal Materials
The characteristics of energy-dispersive semiconductor x-ray spectrometers derive pri-
marily from the properties of the materials used to make the device itself. Although the
most common material for semiconductor detectors in EDXRF is silicon, devices based on
the use of germanium or compound semiconductors such as mercury(II) iodide (HgI2),
CdTe, CdZnTe, or GaAs have also been used to varying degrees. In particular, mercury
(II) iodide detectors (Swierkowski et al., 1974; Slapa et al., 1976; Ponpon and Sieskind,
1996) have been used successfully in both research and commercial products for many
years. Early devices with adequate performance at room temperature were own on space
missions. More recently, devices have been used in hand-held EDXRF spectrometers
where the benet of ambient temperature operation, with or without thermoelectric
(Peltier) cooling of the eld-eect transistor (FET), have been successfully exploited.
Iwanczyk et al. (1996) compared the performance of HgI2, Si PIN photoiodide, and CdTe
detectors for this latter, important application. Large arrays of up to 100 HgI2 detectors
have also been fabricated (Iwanczyk et al., 1995; Patt et al., 1995). Dabrowski et al. (1981)
have been particularly successful in designing, fabricating, and characterizing HgI2 de-
tectors throughout the past two decades and their work should be consulted for further
details of this important type of EDXRF detector. Although high-purity germanium
(HPGe) is widely used for detectors in electron microscopes as a result of its slightly better
resolution than Si(Li) detectors, the use of HPGe detectors is less popular in photon-
excited EDXRF spectrometry. One reason for this lack of acceptance may lie in the high
escape peak intensities (see Sec. III.E.1) which can strongly interfere in trace analysis.
Table 2 lists properties relevant to x-ray detection for Si, Ge, and HgI2, which are the
materials most commonly employed in commercial EDXRF spectrometers. A variety of
other compound semiconductor materials, such as GaAs, CdTe, and CdZnTe, have been
used for applications in which specic properties are particularly benecial. These prop-
erties include the following:
Higher atomic number for increased photoelectric cross section
Larger band gap for lower thermal leakage at room temperature
A lower band gap corresponding to a smaller average energy for creation of
holeelectron pairs (Knoll, 1979), which oers improved energy resolution.
Recalling the direct relationship described earlier between photon energy and number of
charge carriers and, therefore, the detectors signal resulting from detection of a particular
x-ray photon, one can use the data from Table 2 in the following example for detection of
CaKa1 (KL3), which has an energy of 3.691 keV:
No. electronhole pairs produced 3691=3.86 956
Charge on electron 1.661019 C
Therefore,
Charge from CaKa1 interaction 1.5361016 C
Assuming a feedback capacitance in the rst stage amplication of 0.1 pF, the
resulting output voltage pulse is 1.53 mV.
From this, we can see the very small magnitude of the signals involved. This has led to very
great eorts having been made in the design of detector and signal processing systems to
minimize all sources of electronic noise which would otherwise interfere very strongly with
the signal being sought.
In addition to the conventional Si(Li) detector, Si PIN (Haselberger et al., 1996;
Cesareo et al., 1996) and Si drift detectors (Lechner et al., 1996; Bertuccio et al., 1996)
have also become available in recent years. The active area of these devices is generally
Table 2 Semiconductor Detector Material Properties
Detector properties Si Ge HgI2
Atomic number 14 32 80.53

Atomic=molecular weight 28.09 72.60 454.45
Density (300 K) g=cm3 2.33 5.33 6.3
Band gap (300 K) (eV) 1.115 0.665 2.13
Average energy E per electronhole pair (77 kV) 3.86 2.96 4.15a
(eV)
Fano factor (77 K) 0.12 0.08
a
At 300 K.

310 mm2 and the depletion thickness is of the order of 300 mm, which reduces detection
eciency (see Sec. III.F) compared to Si(Li) detectors.
In the following section, the details of detector operation are discussed, with parti-
cular emphasis on those aspects that impact EDXRF spectrometry most directly. These
include the detector energy resolution, detection eciency, spectral response, and counting
system throughput.
C. Cooling Systems
The need to minimize the electronic noise of the detection system is paramount for ob-
taining the best energy resolution. The main source of noise in the detector itself is leakage
current, which derives from the generation of charge carriers in the absence of x-rays
through, for example, thermal vibrations of the detector crystal lattice. Whatever the
cooling system used, the intention of it is to minimize leakage, and the lower the tem-
perature, the less leakage will occur. The boiling point of liquid nitrogen (77 K) is a typical
temperature used for the detector crystal, although the FET may require a dierent and
often higher temperature to minimize its noise contribution and, therefore, obtain opti-
mum detector resolution.
The need for reduced operating temperature results in the need for careful design in
the insulation from ambient temperatures of the detector crystal. Eective insulation is
typically achieved by enclosing the detector head (crystal and FET) assembly in a evac-
uated cryostat. In order for the low-energy x-rays (< 2 keV) to reach the detector crystal,
the vacuum is usually retained by a thin (typically 550 mm) beryllium entrance window
(Fig. 11). In recent years, the thinnest windows (5, 8, and 12 mm) have become available
with coatings which ensure that there is no leakage of He through the Be window. Any
helium getting through the window would degrade the high vacuum within the cryostat
and lead to increased temperature, leakage current, and deteriorating performance.
The original and perhaps simplest way of cooling a detector unit is to attach the
measurement head via a cold-nger assembly to a dewar vessel containing liquid nitrogen
(LN). The dewar itself is typically a complex technological component if it is to provide
high performance and long operational lifetime. The modern LN cryostat delivers opti-
mum resolution and the ability to be cycled through multiple warm-up=cooldown cycles
without degradation in performance. The inevitable and natural boiling-o from the
dewar of LN over a period (1 L per day is typical) means that the dewar needs regular
replenishment. In order to minimize the frequency of replenishing LN, a large dewar is
preferable, although this desire for a long LN holding time may lead to a rather bulky
system. LN volumes of 715 L are typical, although some large systems may use volumes
up to 25 L and some small, hand-held units may use 1 L or less. In any event, the fol-
lowing are important:
Use only liquid nitrogen: Liquid air, although delivering the required temperature
range, will fractionate, yielding O2, which is an explosion hazard in the chemical
laboratory.
Ensure that there is no ice or dirt in the LN used. The presence of ice or dirt in the
dewar can cause microphony, which can degrade energy resolution. Ice and dirt
can be eliminated by pouring the LN through a funnel equipped with a wire
screen (e.g., a motor fuel metal lter funnel).
Observe safe LN handling procedures. Avoid overlling and spillages as liquid
nitrogen can cause embrittlement of polymers and cable insulation or result in
Figure 11 Cross section of a groove-type Si(Li) detector mounted in its cryostat end cap.
condensation from the atmosphere being deposited on components that are

sensitive to moisture.
It is essential that a Si(Li) detector be kept cold throughout the time that the bias is
applied. If this is not done, then there is the possibility of damage to the detector as-
sembly by, for example, migration of the drifted Li ions from the compensated region
of the crystal. Should this happen, the detector will fail and, for this reason, it is usual
for an automatic bias shuto system to be implemented. Such systems typically use a
temperature sensor or a LN level sensor to switch o the detector bias in case of the
dewar warming up. Other detectors, such as HPGe or high-purity Si, for which drifting
is not required, do not exhibit this particular problem but may still suer some pro-
blems if thermally cycled repeatedly, unless the cryostat assembly is specically designed
to do this.
The simplicity of the LN-lled dewar has led to its widespread use in EDXRF systems.
However, the diculty in obtaining LN in remote areas, or the need for a no-LN solution,
has led to the introduction in the past decade or so of thermoelectric (Peltier eect) coolers or
mechanical refrigerating units. The mechanical units may employ the JouleThompson
(JT) eect or some other cycle such as the Stirling cycle to obtain essentially LN temper-
atures at the detector head. The major benet of this approach is that there is no dierence in
performance in terms of detector energy resolution from the conventional dewar LN sys-
tems, but the coolers come with penalties of increased complexity, cost, and bulk. HPGe
detectors, which typically need liquid-nitrogen temperature to operate, may use these me-
chanical coolers, but other detectors which will function at higher temperatures, albeit with
degraded energy resolution, are suitable for use with thermoelectric (Peltier eect) coolers.
Peltier coolers can oer a very compact cryostat=detector assembly that requires
only electrical power to provide its cooling. Multistage (three to six) coolers may be used
to provide a DT cooling, from ambient, of 50 C to a maximum of perhaps 120 C. In an
ambient room temperature of 20 C, such coolers deliver working detector temperatures
typically in the range 30 C to 90 C, which are suitable for Si PIN, HgI2, and extremely
low-leakage Si(Li) detectors. Energy resolution in the range 200350 eV (see Sec. III.D) is
typically available with these systems and both Si PIN and HgI2 detectors are commer-
cially available with Peltier cooling. More recently, Peltier-cooled Si drift detectors, which
oer energy resolution better than 150 eV, have been developed (Lechner et al., 1996;
Bertuccio et al., 1996) and are now commercially available.
D. Energy Resolution
The energy resolution of the semiconductor spectrometer system determines the ability of
a given system to resolve characteristic x-rays from multielement samples. It is normally
dened as the full width at half-maximum (FWHM) of the pulseheight distribution
measured for a monoenergetic x-ray at a specied energy. A convenient choice of x-ray
energy at which resolution is quoted is the weighted mean MnKa line at 5.895 keV, as this
emission line is readily available from 55Fe radioisotope sources. The MnK x-rays are of
suciently low energy that the contribution to the FWHM of the unresolved Ka1 Ka2
doublet (5.898 and 5.887 keV, respectively) and the intrinsic width of the emission lines
can be neglected. This is not true for higher-energy characteristic x-rays (e.g., MoK lines)
for which the separation of the Ka1 Ka2 doublet and the intrinsic width of the emission
line must be considered. Figure 12 shows a typical pulseheight spectrum of MnK x-rays
taken from an 55Fe source.
Typical state-of-the-art 30-mm2 Si(Li) detectors achieve a FWHM better than
140 eV at 5.9 keV, although values as low as 130 eV are achievable. However, this number
is but one indicator of the quality of an EDXRF detector system, and other factors such as
maximum count rate or the presence of background and artifacts may be more important
in many analytical applications. Peltier-cooled Si PIN detectors oer FWHM values
typically in the range 165220 eV, whereas Si drift detectors claim < 150 eV. The inter-
dependence of energy resolution and count rate is discussed below, although it is worth
noting at this point that the user can exert a large degree of control over this by making an
appropriate selection of pulse processor settings.
If one neglects the natural linewidth of the x-ray lines, the instrumental energy re-
solution of a semiconductor detector x-ray spectrometer is a function of two independent
factors. One of these is determined by the properties of the detector itself; the other is
dependent on the nature of the electronic pulse processing employed. In some systems,
a pulser or strobe signal may be injected into the measurement system in order to monitor
the resolution of the electronic system independent of any peak broadening due to the
detector itself.
The measured FWHM of the x-ray line (DETotal) is the sum, in quadrature, of the
contribution due solely to detector processes (DEDet) and that associated with the elec-
tronic pulse processing system (DEElec):
q
DETotal DE2Det DE2Elec 1
The DEDet component is determined by the statistics of the free-charge production process
occurring in the depleted volume of the diode. The average number of electronhole pairs
Figure 12 Pulseheight spectrum of MnK x-rays taken with a 30-mm2 Si(Li) detector.
produced by an incident photon can be calculated as the total photon energy divided by the
mean energy required to produce a single electronhole pair (see Sec. III.B). If the uc-
tuation in this average were governed by Poisson statistics, the standard deviation would be
r
p E
s n 2
e
In semiconductor devices, the details of the energy-loss process are such that the individual
events are not strictly independent and a departure from Poisson behavior is observed.
This departure is taken into account by the inclusion of the Fano factor in the expression
for the detector contribution to the FWHM:
r
p FE
s Fn 3
e
Taking
sE p
Fn 4
E
and, rearranging,
p
DEDet 2:35 FeE 5
where e is the average energy required to produce a free electronhole pair, E is the energy
of the photon, F is the Fano factor (see Table 2), and the factor 2.35 converts the standard
deviation to FWHM for a Poisson distribution.
A typical value for the detector contribution to resolution, also known as the disper-
sion, is 120. Examination of the values of e and F listed in Table 2 shows that for an
equivalent energy, the detector contribution to the resolution is 28% less for the case of Ge
compared to Si. This results in better energy resolution being obtained for HPGe detectors
and could be an important consideration in the choice of detector for certain applications.
However, this theoretical advantage in energy resolution of Ge over Si(Li) is mitigated
in many systems because of the dominance of electronic noise (e.g., from the FET). In ad-
dition, the very high GeK escape peak probability (see Sec. III.E.1) is likely to be a serious
limitation to the use of HPGe detectors in most EDXRF work. HPGe detectors are widely
used in electron microscopes, where energies < 10 keV are likely to be of most interest.
E. Spectrum Artifacts
The simplicity of the element line spectra encountered in XRF spectrometry is one of its
major benets when compared with other atomic spectroscopy methods. However, a few
peaks can arise in the EDXRF spectrum from sources other than the elements in the
sample and it is wise to be aware of their nature. Unlike basic detector eciency and
spectrum background, which are dened by the selection of detector window and the
detector manufacturing process, the end user can exert some control over the eects of
spectrum artifacts. From the spectra presented so far, it is clear that the bremsstrahlung
continuum and the Compton (and Rayleigh)-scatter peaks arise from the interaction of the
exciting radiation with the sample. These features are not regarded as artifacts.
1. Escape Peaks
For an incident x-ray with energy higher than the SiK absorption edge, the detection
process will involve the generation, through x-ray uorescence of the detector material, of
SiK x-rays. The vast majority of these will themselves immediately be absorbed in the
detector volume and contribute to the overall charge collected for the original incident
x-ray photon. This is the normal mechanism of x-ray detection, which was described
earlier. There is, however, a nite probability that the SiKa x-rays produced will escape
from the detector volume and not contribute to the charge collected for the original
photon that was detected. The resulting energy detected will be reduced by 1.740 keV,
which is the energy of the SiKa x-ray that escaped. The greatest probability of escape arises
close to the front of the detector crystal from which SiK x-rays can more easily escape.
X-rays detected far within the volume will still generate SiK x-rays, but they will all be
absorbed before they can reach the outer surface of the crystal and escape. The probability
of generating the SiKb x-ray and of it escaping is extremely low and this eect can safely be
ignored. The result of the SiK escape process is a peak in the collected spectrum, which is
1.74 keV lower in energy than the parent peak. The Si escape peaks for TiKa and TiKb are
clearly seen, 1.74 keV below the TiK lines, in Figure 13 (indicated by 1 and 2, respectively)
(see also Table 3). In many detectors, the incomplete charge-collection tail on the low-
energy side of the parent peak will obscure the Si escape peak from TiKb.
The escape probability is highest for lines closest to the SiK absorption edge at
1.838 keV and may be calculated as described by Statham (1976) and Dyson (1974). The
intensity falls rapidly from around 3% of the parent peak at 23 keV to around 0.1% of
the parent peak at 10 keV. At energies above 10 keV, the eect is negligible, but below this
energy, it is important that spectrum-processing software takes account of the peak.
Typically, the processing software will make a correction in which the Si escape peak
is removed and the most comprehensive packages will reinstate the lost intensity to the
parent peak. If such packages are available, then make use of them before carrying out
Figure13 Peak artifacts from a Ti spectrum collected by a Si(Li) detector (see Table 3 for details).
qualitative analysis in order to avoid classic errors such as the Si escape peaks from ZnK
being identied as Co!
In the case of HPGe, the escape probability for GeL lines is negligible in XRF and
can be ignored. The escape of the GeK lines has, however, a very high probability, and for
Se, the escape peak intensity is around 16% of the parent peak. This is due to the com-
bination of the high detector eciency for GeK x-rays and the much greater depth within
the crystal from which the GeK lines can escape. There is further complication in that
there are many GeK lines and each of these lines will result in an escape peak. The
complexity and intensity of Ge escape peaks can easily be seen in the spectrum from a
molybdenum oxide sample, shown in Figure 14.
The principal GeK lines and their characteristic energies are as follows:
GeKa: 9.876 keV
GeKb1: 10.981 keV
GeKb2: 11.100 keV
The assignments of the numbered GeK escape peaks arising from the detection of the
MoK lines are listed in Table 4.
Table 3 Artifact Peak Energy and Assignments for Figure 13
Peak No. Energy (keV) Assignment
1 2.8 TiKaSiK escape

2 3.2 TiKbSiK escape
3 9.0 TiKa TiKa sum peak
4 9.4 TiKa TiKb sum peak
5 9.9 TiKb TiKb sum peak

Figure 14 GeK escape peaks from Mo spectrum collected by HPGe detector (see Table 4 for
details).
The energy and intensity of these GeK escape peaks interferes very strongly over a
wide and important region of the spectrum. The interference is considerable from the GeK
escape peaks of Nb and Mo in stainless steels and corrections for these intense escape
peaks are not suciently accurate to retain the intrinsic performance of EDXRF for what
would be a reliable and straightforward analysis using a Si(Li) detector. The severe lim-
itation posed by the Ge escape peaks in EDXRF is also demonstrated in Figure 15 (see
also Table 5) for a typical determination of minor and trace heavy metals in a low-Z
matrix. In this case, the complex GeK escape peaks from the Rh backscatter peaks
completely dominate the important part of the spectrum for trace analysis.
In conclusion, the Si escape peak is small and easily corrected, but the number and
high intensity of the GeK escape peaks severely limit the value of the HPGe detector for
tube-excited EDXRF. In the case of energy-dispersive (ED) microanalysis, however,
Table 4 GeK Escape Peak Assignments and Relative Intensity for Figure 14
Peak No. Energy (keV) Assignment % of parent
1 6.4 MoKaGeKb1 1.5

2 7.57 MoKaGeKa 9.6
3 8.6 MoKbGeKb 1.0
4 9.74 MoKb1GeKa 8.8
5 10.12 MoKb2GeKa 2.5

Figure 15 Comparison of Si(Li) and HPGe detectors for tube-excited EDXRF trace analysis of
low-Z sample matrix (see Table 5 for details).
the HPGe detector has benets in that the intensity of the GeL escape peaks is negligible
and the energy resolution is better than that of Si(Li) detectors.
2. Sum Peaks
Sum peaks arise from a specic form of peak pileup (see Sec. IV.C) where two events from
high-intensity peaks arrive in the pulse processing electronics so close together in time that
the pileup inspector cannot recognize them as two events. The eect of this is for the signals to
be seen as one and for them to be registered at the energy that is the sum of the two. The sum
peaks of Ti are seen in Figure 13, in which the most intense peak (3) is from the sum of two
TiKa events. The smallest peak (5), from the sum of two TiKb events is only visible when the
parent peak is very intense. At rst glance, peaks 3 and 4 may appear like a typical Ka, Kb
Table 5 GeK Escape Peak Assignments for Figure 15
Peak Assignment
1 RhKa ComptonGeKa
2 RhKa RayleighGeKa
3 RhKb ComptonGeKa
4 RhKb RayleighGeKa

doublet, but the peak separation is too small for K lines in the region of the spectrum in which
they occur. In addition, the relative line ratio is not the same as for a characteristic K line
series at this energy. Consequently, sum peaks are unlikely to be incorrectly identied as
elements, but they may interfere with important lines in a particular analysis. This is parti-
cularly the case in some environmental analyses, (e.g., where high concentrations of Fe lead
to intense FeK lines). This will result in FeK sum peaks in the region of the K lines of Se and Br
and the L lines of toxic heavy elements such as Hg, Tl, and Pb.
Some spectrum-processing software packages are able to correct for sum peaks and
should be used to minimize potential errors in analysis (See Chapter 4). If it is found that
such features are not available, then reducing the count rate will substantially reduce the
eect of the sum peaks. In order not to lose analytical performance, however, selection of
alternate excitation conditions (e.g., using a more absorbing beam lter) will rebalance
the spectrum in favor of the peaks at higher energy and minimize the interference.
3. Diffraction Peaks
Whenever a crystalline sample is measured in an EDXRF spectrometer, there is the
possibility that the conditions for Bragg diraction will be met. This is exacerbated by the
divergent geometry of the incident and detected beam and the variety of excitation con-
ditions available. The worst cases are where unltered primary radiation is used, as there
are then many energies and angles which increase the probability of meeting the Bragg
condition for a crystalline component in the sample. The more monochromatic the ex-
citing beam is, the less likely it is that the Bragg condition will be met. Figure 16 shows the
diraction peak obtained from a boric acid pellet which was excited with a silver anode
x-ray tube operated at 5 kV with no primary beam lter and in an approximately 90
geometry.
The spectrum is overlaid with one from a sulfur pellet measured under exactly the
same conditions. It can be seen that the diraction peak is broader than a K series line at
that energy and the low-energy tailing is more pronounced. There is some possibility for
misidentication, but the most likely problem arises in any spectrum processing not setup
to take account of this peak. In cases such as silicon wafers, where the crystal planes are
highly oriented, the sample can be tilted or rotated to minimize the often sharp diraction
peaks that can be observed. Alternatively, eective use can be made of additional colli-
mation to constrain more closely the angles that can satisfy the Bragg condition or of
alternate excitation conditions, which change or reduce the incident energies available for
diraction. Figure 17 shows a comparison of the spectra taken from the same two samples
under dierent excitation conditions.
The increased kV and use of an absorption lter completely change the energy
distribution of the excitation spectrum and eliminate the diraction peak. This second set
of conditions is particularly eective for lines in this part of the spectrum and eectively
removes problems from diraction peaks. Once a diraction peak is identied as causing a
problem, a change of excitation conditions is often the best measure to adopt. The use of
monochromatic or polarized excitation or of secondary targets in Cartesian geometry will
also eliminate diraction peaks.
4. System Contamination Peaks

Careful screening of all the components in an EDXRF spectrometer is required in order to
eliminate spurious element peaks in measured spectra. Each spectrometer designer will
adopt dierent approaches and materials for this purpose and, thus, there is a variety of
Figure 16 Spectrum from boric acid, overlaid with one from a sulfur pellet, showing the
diffraction peak. Conditions: Ag target x-ray tube, 5 kV, no primary beam filter.
Figure 17 Spectrum from boric acid, overlaid with one from a sulfur pellet, showing removal
of the diffraction peak seen in Figure 16. Conditions: Ag target x-ray tube, 15 kV, thin Al primary
beam filter.

potential spectrum contaminant peaks. Careful design will eliminate them, although, in
some cases, the use of a simple blank correction may be required in some trace analysis.
Detector components can be a cause of some system peaks. Beryllium entrance
windows usually contain some trace elements that, in extreme cases such as TXRF, can be
seen in blank spectra. The use of thick beryllium windows exacerbates this potential
problem, but window thicknesses commonly used (850 mm) should pose no practical
problem. The Si internal uorescence peak and absorption edge caused by the dead layer
are eects not seen in practice and need very careful characterization with specialized
conditions if they are to be seen at all.
The most likely source of spurious spectrum peaks is sample handling and pre-
sentation, both of which are largely in the control of the user.
F. Detection Efficiency and Entrance Windows

One of the more important advantages of semiconductor spectrometers is the absolute
eciency with which uorescence x-rays are detected and their energies measured. This is
the result of the intrinsically high photoelectric absorption eciencies for semiconductor
materials in the x-ray energy range and from the large solid angles achieved in typical
EDXRF geometries. The solid angle is determined by the area of the detector and the
sampledetector distance and varies with the design of the system. Typical areas are
1080 mm2 for Si(Li) detectors. Although the additional solid angle is advantageous for
many applications, one must realize that the added capacitance associated with increased
active area results in an increased contribution in the electronic noise of the system. This,
in turn, results in an increased energy resolution of the detection system.
The intrinsic eciency of the semiconductor device can be approximated by a simple
model in which the probability of detecting an x-ray incident on the detector is assumed to
be the probability of photoelectric absorption within the sensitive volume. This can be
expressed as
eE emt 1 esd
where e(E) is the energy-dependent intrinsic eciency of the detector, t is the thickness of
any absorptive layer between the sample and the detector, m m(E ) is the mass absorption
coecient of the absorptive layer, d is the detector thickness, and s s(E ) is the photo-
electric mass-absorption coecient for the detector material. Figure 18 shows plots of the
above equation for the case of a 3-mm-thick Si(Li) and a 5-mm-thick HPGe detector.
The poor eciency at low energies is assumed to be determined by the combined
absorption of the 25-mm beryllium entrance window and a nominal 2-cm air pair between
sample and detector. The energies of the characteristic K emission lines for several
elements are also shown. The plots show the near-unity intrinsic eciencies for both
detectors over a wide range of useful x-ray energies. The Ge detector is ecient at much
higher energies than Si because of the higher atomic number and subsequent larger
photoelectric cross section.
The simple model gives a semi-quantitative picture of the eciency behavior of
semiconductor spectrometers. However, several other factors must be considered for
quantitative calibration of a uorescence spectrometer. The concept of a thin entrance
window that either absorbs or transmits an incident x-ray does not describe cases in which
the secondary electrons, either photoelectric or Auger, are emitted into the active volume
from the window layer. Similarly, detailed studies of the low-energy eciency have in-
dicated the presence of an absorbing layer on the surface of both Si and Ge devices
Figure 18 Calculated intrinsic photopeak efficiency for Si and Ge detectors as a function of
incident photon energy. The high-energy limits are established by the photoelectric cross section of
the detector material and the diode thickness. The low-energy cutoff is determined either by
absorption in the thin Be window or in a nominal 2-cm air path from sample to detector or
fluorescence source.
associated with the surface layer of the semiconductor material itself. This layer is com-
prised of an evaporated metal contact used to form the rectifying Schottky barrier and a
thin surface layer (the dead layer) of inactive semiconductor material from which charge
cannot be collected. The thickness of evaporated metal, normally Au, can be determined by
direct measurement during the manufacturing process and is typically in the range of 10 nm.
The eective dead layer of semiconductor material is a more complicated parameter to
determine. Empirical studies have attempted to measure the absorption inherent in the
semiconductor surface layer. Such studies established that the eective thickness is de-
termined largely by the absorption length of the low-energy photons and the charge-
transport characteristics of the associated ionization products. In the simplest model, there
is competition from the rate of diusion of the electronhole distribution, against the
gradient of the applied eld. For distances near the entry contact, a part of the charge can
diuse into the contact and be lost to the signal before the electrical eld can sweep it to the
opposing electrode. This loss of charge can be interpreted in terms of an eective window
thickness of typically 0.2 mm silicon equivalent. In addition, thin evaporated contacts are
deposited on the entry surface that can absorb incident low-energy photons.
Detailed experiments have indicated that the charge-collection eciency for events
near the surface depends in a complex way on low-energy x-ray and charge-transport
properties (Llacer et al., 1977; Goulding, 1977). As a consequence of these entry-window-
related eects, the eciency for low-energy photons can be reduced. The events lost from
the photopeak can then appear in a continuum background below the full-energy peak,
where they reduce detectability and interfere with spectral analysis. Similarly, secondary
electrons or photons originating from the photoelectric absorption events that occur in-
itially in the active volume can escape. This results in a collected charge pulse of reduced
amplitude. An easily observed manifestation involves the observation of discrete peaks in
the spectrum. Continuous-loss processes involving electron escape can also occur, al-
though the probability is small. These and related mechanisms that reduce the amplitude
for a given event can lower the photopeak eciency relative to the simple model described.
There have been studies in which the eciencies of Si(Li) and Ge have been carefully
measured using calibrated sources of x-rays spanning the energy region of interest (Cohen,
1980; Szoghy et al., 1981; Campbell and McGhee, 1986). These indicate that the maximum
intrinsic photopeak eciency is reduced by a few percent relative to the curves shown in
Figure 18 and is slightly higher at the upper energy cut o than calculated. These results
substantiate the overall validity of the simple photoelectric absorption model but de-
monstrate the limitations if precise results are required. For laboratory applications of
EDXRF, it is not necessary to explicitly determine the photoelectric eciency function
because it is included in the overall calibration factor of the instrument. In any event, the
internal eciency of the detector itself is dened by the design and manufacture of the
detector and this is out of the control of most users.
The eciency curve shown in Figure 18 illustrates that for conventional EDXRF
measurements, the absorption of uorescence x-rays in air and in the Be entry window
limits the accessible energy range to photons greater than approximately 2 keV. The ab-
sorption losses in the air path can be signicantly reduced by the common practice of
employing a vacuum or He atmosphere. A vacuum path is preferable due to higher x-ray
transmission, and if helium is used, the beryllium entrance window must be able to
eliminate leakage into the cryostat with subsequent loss of its vacuum. Coated beryllium
windows are commonly used nowadays to minimize helium leakage into the cryostat.
The necessity of a beryllium window to maintain vacuum integrity between the
cryostat enclosure and atmospheric pressure does not constitute a serious limitation for
most analyses. However, there are applications in which the detection of x-rays with en-
ergies below 1 keV (e.g., for F) becomes necessary. The relatively high detection limits
achieved by EDXRF systems because of the poor energy resolution (compared with
WDXRF) combined with absorption by the beryllium window generally make EDXRF
the second choice for these very low-energy x-ray lines. A beryllium window thickness of
8 mm is typically used for very light-element analysis, although windows as thin as 5 mm
have been used. The use of extremely thin windows may lead to increasing concerns for
helium integrity and equipment cost.
High-strength thin windows made from low-atomic-number elements that are cap-
able of withstanding a full 1-atm-pressure dierential have become commercially available
in the last decade. These include self-supporting 0.5-mm diamond polycrystalline lms
and 0.25-mm windows composed of a vapor-deposited amorphous material consisting of
90% boron by weight with nitrogen and oxygen for the remainder. These windows
exhibit signicant x-ray transmission for photons well below 1 keV and have found
widespread use in x-ray microanalysis.
G. Detector Background
Eects associated with the partial collection of the photoelectric signal by the detector
have a small eect on its eciency. However, these incomplete charge-collection processes
can have consequences that are far more serious for analytical performance through their
eect on spectral background. The eect of incomplete charge collection of these events is
to produce tailing on the low-energy side of a peak. In addition, it produces a continuum
of events that appear as a shelf on the low-energy side of major peaks in the spectrum. This
background tailing and shelf interfere with the measurement of lower-energy uorescence
x-rays and is a signicant factor in obtaining the lowest detection limits for the determi-
nation of trace quantities on the low-energy side of major peaks.
Studies designed to reduce this background have indicated that in addition to
fundamental x-ray and electron-energy-loss processes, a more signicant background
resulting from incomplete charge collection from the detector active volume is normally
the dominant contribution (Goulding et al., 1972; Jaklevic and Goulding, 1972). This
process is an artifact of the detector operation in which the collection of the free charge
from the depleted volume is inhibited as a result of nonuniformities in the applied
electrical eld. These nonuniformities are typically associated with edge eects at the
periphery of the cylindrical detector. The incomplete charge-collection background can
be reduced either by external collimators that prevent the incident radiation from in-
teracting in the periphery of the detector or by internal electronic collimation brought
about by the use of a guard-ring structure (Goulding et al., 1972). The tailing can
sometimes be improved by increasing the detector bias, but this is not an option
available to the majority of users. There has been much work on characterizing the
detector line shape and the eects on background and tailing of incomplete charge
collection (Campbell and Wang, 1991; Campbell et al., 1997; Heckel and Scholz, 1987;
Lepy et al., 1997). Such studies have led to a greater understanding of the processes
involved and to peak-tting procedures that can take account of them. However, im-
provements in this form of background can only be achieved through improvements in
detector design and manufacturing processes.
The P=B ratio of a detector is a standard measurement of detector quality. The
measurement is made using a 55Fe radioisotope source to ensure that there is no other
contribution to background. The measurement cannot be made using x-ray tube excita-
tion, as it is extremely dicult to eliminate the residual bremsstrahlung continuum. The
peak is taken from the most intense channel in the MnKa peak and the background is
taken as the average intensity in the channels from 0.9 to 1.1 keV. A high-quality Si(Li)
detector will deliver a P=B ratio in excess of 10,000:1 and have minimal low-energy tailing.
IV. SEMICONDUCTOR DETECTOR ELECTRONICS

A. Sources of Electronic Noise
The contribution to resolution associated with electronic noise (DEElec) is the result of
random uctuations in thermally generated leakage currents within the detector itself and
in the early stages of the amplier components. Although these processes are intrinsic to
the overall measurement process, there are methods for limiting the impact on the nal
system resolution. Figure 19 is a schematic diagram of a typical pulse processing system
employed in a semiconductor detector x-ray spectrometer. The pulse processing can be
divided between the charge integration, which takes place in the preamplier, and the
voltage amplication and pulse shaping, which occur in the main amplier (pulse
processor).
The function of the charge-sensitive preamplier and subsequent amplication stages
is to convert the integrated charge pulse, produced by collection of the photoelectrically
induced ionization, to a voltage pulse that can be measured and stored in the multichannel
pulseheight analyzer (MCA). The rst stage of the process occurs in the FET, which is
attached to the rear of the detector crystal. The method of charge restoration used for the
FET has a fundamental eect on the electronic noise of the overall detection system and is
Figure 19 Typical pulse processing system used for energy-dispersive detectors.
particularly important. Early detectors used pulsed optical charge restoration, but newer
systems make use of integrated solid-state devices incorporating low-noise-junction FETs
to minimize electronic noise (Statham and Nashashibi, 1988; Lund et al., 1995, Lund et al.,
1996). However, the pulse processing must also achieve a very important goal of ampli-
fying the weak charge signal to a measurable level while suppressing random uctuations
in the signal amplitude produced by thermal noise. This is achieved by generating a
carefully dened pulse shape in the main amplier, which restricts the Fourier frequency
components in the nal signal in such a way that the signal contributions are emphasized
relative to the noise uctuations.
The most common pulse shapers employed in modern semiconductor spectro-
meters generate output pulses that are Gaussian, triangular, or cusp shaped (Fairstein
and Hahn, 1965; Kandiah et al., 1972; Landis et al., 1982). Each is capable of achieving
adequate energy resolution for EDXRF analysis; the dierences are due mainly to the
eective time interval required for processing a pulse. Because the relative amplitude of
the noise contribution is a strong function of the characteristic time constant associated
with the pulse shaper, the dierence between pulse shapes becomes important for ap-
plications in which high counting rates are important. A detailed analysis of the eects
of various pulse-shaping options on spectrometer performance is presented by Goulding
and Landis (1982). More recently, suciently fast, sampling analog-to-digital converters
(ADCs) have become available and these have resulted in the availability of digital pulse
processors (Warburton et al., 1988). These devices can implement the optimum noise-
reduction lters in conjunction with much higher count rates than conventional analog
pulse processors.
As pointed out below in the following subsection, however, it is not always desirable
to operate at the minimum-noise shaping time because an unacceptably large dead time
may result. Although EDXRF instruments are designed with a suitable compromise be-
tween energy resolution and count rate capabilities, an understanding of these trade-os
on the part of the user is important for optimum usage of the instrument.
B. Resolution and Count Rate
There exists a great deal of literature on the nature of the detection and pulse processing
systems and the great strides which have been made over the past 20 years to improve
resolution and increase count rate. For many years, the complete integration of the de-
tection and electronics systems within the instrumentation has meant that the individual
choice of and matching by the EDXRF user of detector, main amplier, ADC unit, and
MCA is no longer required. Once the application is determined, the choice of system will
typically revolve around achievable analytical performance.
The user will typically be left with a relatively straightforward selection of the single
signal processing setting providing the required resolution and count rate
(see Fig. 20). There is only a single setting and, unfortunately, resolution and rate go in
opposite directions when this setting is changed. In one direction, the amplier time
constant will increase, which gives better resolution (lower FWHM) at the expense of a
lower count rate into the MCA memory. In the opposite direction, resolution degrades but
count rate increases. Once the EDXRF system is chosen, this control is really the only way
in which the user can inuence resolution and count rate.
It is a little like choosing a car where you select the type of vehicle most suited to
your use. That vehicle then has a gearing selection system that allows you some degree of
trade-o in control. Low gears give highest accuracy in maneuverability (i.e., resolution)
but lowest speed (i.e., count rate). Conversely, the highest gears give a high speed (rate)
at the expense of accurate maneuverability!
At one end of the range, best resolution is obtained with lowest total count rate,
whereas at the other, highest count rate is delivered with the worst energy resolution.
When severe peak overlap is the dominant limitation to analytical performance, the best
resolution should be selected. In this case, which is typical for the light elements, the
Figure 20 Plots of energy resolution (at 5.9 keV) and count rate for a Si(Li) detector.

excitation conditions will need adjusting to make best use of the limited count rate
available. Where peak separation is good, such as above 15 keV, or where there are no
severe overlaps, select the fastest count rate. In both cases, the current is used to adjust for
optimum dead time (50% typically) and the measurement time is used to control the
precision.
C. Pulse Pileup
The count-rate limitations associated with a semiconductor spectrometer are an inherent
property associated with the nite pulse processing time required by the electronic shaping
network. When a random sequence of pulses is incident on the detection system, some of
the events cannot be processed without ambiguity. To appreciate the fundamental nature
of this limitation and its relationship to system performance, some elementary concepts of
electronic pulse processing must be considered.
Figure 21 illustrates the time sequence of pulses that occur at various stages in the
pulse processing chain. Trace A shows the output of the charge-integrating preamplier.
The steps at times 1, 2, and 3 represent the charge integrals of discrete events. Traces B and
C are the outputs of the fast (short shaping time) amplier and an associated discriminator
that serves as a timing marker for the individual events. The main shaping amplier output
is shown as the Gaussian pulse shapes (in trace D). For each event, a total pulse processing
time (neglecting analog-to-digital conversion in the pulseheight analyzer) of td is re-
quired after the arrival of the pulse and before the system is ready to accept the next event.
Although the average counting rate detected by the system can be well below the
frequency dened by the reciprocal of the pulse width td, that the events are statistically
uncorrelated implies that the events are not uniformly distributed in time. There then
exists a probability that two pulses will occur within the same processing time interval.
This is illustrated by the overlap of pulses 2 and 3 in the trace.
At a low average counting rate, this pulse overlap is not a limiting factor. As the
average counting rate increases, however, a point is reached at which there is a signicant
probability that a second event will occur before the rst event has been fully analyzed.
If the two events occur within a time less than the shaping time of the amplier, the charge
signals are indistinguishable and an erroneous pileup energy signal results.
Modern spectrometers employ some form of rejection circuitry to eliminate these
pileup events from the pulseheight spectrum. Typical systems rely on the inspection of
the fast discriminator output to determine if two pulses have occurred in rapid succes-
sion. Appropriate logic is then employed to gate the output of the processor to eliminate
the resultant ambiguous energy signals. This is shown in traces E and F of Figure 21, in
which the logic signal causes the output to be inhibited when the pulses overlapped to
produce an ambiguous pileup energy output. Because the fast shaper that generates the
discriminator output has inherently poorer energy resolution relative to the slow channel,
the pileup rejection circuit is limited in the minimum energy of pulses it can detect.
However, in typical tube-excited EDXRF, the major fraction of pulses occur from
scattered high-energy radiation and a pileup rejector system is an important feature in
the system design.
The pileup probability is obviously a function of the characteristic shaping time tp,
which, in turn, establishes the eective dead time, td, of the system. This probability is
independent of the details of the specic type of pileup rejection circuit used to eliminate
the ambiguous events. The number of events that experience pileup and are consequently
eliminated from the spectrum can be estimated for the case of a totally random arrival
Figure 21 Time sequence of pulses during the processing of a series of x-ray events; (A) the output
of the preamplifier is represented as a series of voltage steps reflecting the integrated charge from the
individual events; (B) the output from a fast shaping amplifier that operates with a shorter time
constant than the main shaping system; (C) a fast discriminator timing pulse derived from B; (D) the
output of the main shaper, with the pileup of pulses 2 and 3 indicated; (E) the dead-time gates; and
(F) the final output with the ambiguous 2 and 3 pileup pulses rejected.
distribution. For a series of events randomly distributed in time with an average frequency
N0, the probability P that no pileup events occur within a characteristic time td after a
given event can be expressed as
P N0 eN0 td
From this expression, we can calculate the fraction of events transmitted through the
system. Figure 22 is a plot of nonpileup output rate versus input rate expressed in terms of
a characteristic pulse processing time.
The input rate for which the output rate is a maximum is seen to be the reciprocal of
the shaping time. The output rate at this point is reduced by a factor of 1=e. It should be
emphasized that this behavior is a fundamental consequence of random arrival statistics
and a nite measurement time. However, one should be aware that it is always possible to
reduce the characteristic processing time to achieve an increase in counting rate at some
sacrice in energy resolution. It is also worth noting that, by working at too high a dead
Figure 22 Nonpileup output rate (N0) as a function of input rate (N1) scaled as a function of
a characteristic shaping time. Maximum output is 0.37 of the input rate that is equal to the reciprocal
of the time constant.
time, the throughput curve inverts and the output rate begins to fall. Further increase
of the dead time will eventually lead to paralysis of the system and negligible output
countrate.
Although dierent algorithms can be used to correct for events lost to pileup, there
is no way to eliminate the eect through passive pulse processing (Gedcke, 1972; Hayes
et al., 1978; Statham, 1977). Because dierent manufacturers of x-ray equipment vary in
their approaches to pileup rejection, the only way to evaluate the throughput of the system
is using a variable intensity source of radiation. The input rate can be determined by
scaling the fast discriminator output, which is sometimes available from the instrument
data system. The output rate can be simultaneously measured in the pulseheight ana-
lyser. A plot of nonpileup output rate versus input rate can then be generated and com-
pared to the ideal case shown in Figure 22.
When the excitation source can be switched o in a time interval that is short com-
pared to the characteristic pulse processing time, it is possible to increase the average output
counting rate by eliminating the eects of pileup. Such pulsed excitation systems rely on the
ability to detect an event in the fast channel and to shut o the excitation before a second
pileup event can occur. In this mode of operation, the output rate can equal the input rate
up to the point at which the system is continuously busy. This method of pileup control has
been implemented using pulsed x-ray tubes (Jaklevic et al., 1976; Stewart et al., 1976),
although the increased complexity of the electron optics tends to lead to increased cost.
D. Dead-Time Correction
The presence of pulse pileup must be considered in any system designed for quantitative
measurements because it causes the eciency with which pulses are processed to be rate
dependent. EDXRF analytical systems are designed to correct for this discrepancy
through a variety of approaches. The most straightforward involve the use of a live-time
clock consisting of a gated oscillator and scaler. The oscillator clock is turned o when the
system is busy processing pulses. In this way, the duration of the measurement in terms of
a live-time interval is extended to correct for those periods when the system is incapable of
processing a pulse. Alternative methods rely on the direct measurement of the fast dis-
criminator pulses to keep track of those events that were missed. An additional correction
is added to compensate for those intervals in which pileup occurs (Bloomeld et al., 1983;
Hayes et al., 1978).
A simple empirical method used to correct for dead-time losses is a measurement of
the ratio of input to output counts as a function of input rate over the range of values
normally encountered. Subsequent analyses require that the input rate be measured for
each experiment. The live-time correction can then be applied using the previously de-
termined response function.
Because all live-time correction methods have some limitation on the range of
counting rates over which they can be used, it is important that methods be devised to
evaluate the precision with which such corrections are generated. A carefully prepared
series of standards of varying concentrations represents a direct approach. A potentially
more precise method involves the use of a single thin-lm standard. Variable-mass targets
are placed behind the standard to vary the total counting rate over the range of interest.
If the variable mass target is chosen so that the variable intensity of scattered or uor-
escence radiation does not induce uorescence in the thin-lm standard, the measured
intensity of uorescence from the standard should be independent of total counting rate.
The ability of the dead-time correction system to compensate for pileup can then be
empirically evaluated. All modern EDXRF systems incorporate eective dead-time cor-
rection circuitry, which is likely to be at least as accurate as experiments designed to test
this standard feature.
V. SUMMARY
The technology that makes chemical analysis with EDXRF practical is based on the use of
semiconductor x-ray detectors and associated pulse processing and data acquisition sys-
tems. The present chapter attempted to explain to the analyst the basic concepts behind
the operation of these components and the manner in which they inuence overall system
performance. The trade-os one must make between such parameters as excitation con-
ditions, detector resolution, count rate, and other design variables determine how eec-
tively one can tailor a given instrument or experimental apparatus to a specic application.
Furthermore, a thorough understanding of the factors that limit performance should
enable one to implement experimental tests to determine the eectiveness of a particular
approach and evaluate various commercial options.
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3

Energy-Dispersive X-ray Fluorescence

Copyright 2002 Marcel Dekker, Inc.

II. X-RAY TUBE EXCITATION SYSTEMS

In EDXRF spectrometry, there is no physical discrimination of the secondary radiation

Figure 1 Basic components of a tube-excited EDXRF instrument.

Copyright 2002 Marcel Dekker, Inc.

A. Direct and Filtered Direct Excitation

B. Primary Beam Filter Selection

Table 1 Typical Primary Beam Filters and Their Range of Use

Filter Thickness kV range Elements Comments

No filter N=A 450 All, NaCa Optimum for light elements

Copyright 2002 Marcel Dekker, Inc.

C. Secondary Target Excitation

Copyright 2002 Marcel Dekker, Inc.

Figure 8 End-window x-ray tube.

Copyright 2002 Marcel Dekker, Inc.

A. Fabrication and Operating Principle

Table 2 Semiconductor Detector Material Properties

Detector properties Si Ge HgI2

Atomic number 14 32 80.53

Copyright 2002 Marcel Dekker, Inc.

condensation from the atmosphere being deposited on components that are

Table 3 Artifact Peak Energy and Assignments for Figure 13

Peak No. Energy (keV) Assignment

1 2.8 TiKaSiK escape

Copyright 2002 Marcel Dekker, Inc.

Peak No. Energy (keV) Assignment % of parent

1 6.4 MoKaGeKb1 1.5

Copyright 2002 Marcel Dekker, Inc.

Table 5 GeK Escape Peak Assignments for Figure 15

Copyright 2002 Marcel Dekker, Inc.

4. System Contamination Peaks

Copyright 2002 Marcel Dekker, Inc.

F. Detection Efficiency and Entrance Windows

IV. SEMICONDUCTOR DETECTOR ELECTRONICS

Copyright 2002 Marcel Dekker, Inc.

Aitken DW. IEEE Trans Nucl Sci NS-15:10, 1968.

Copyright 2002 Marcel Dekker, Inc.

Copyright 2002 Marcel Dekker, Inc.

Copyright 2002 Marcel Dekker, Inc.

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