DK1838 - ch02 Chapter 2 (Two) Handbook of X Ray Spectrometry

2
Wavelength-Dispersive X-ray Fluorescence
Jozef A. Helsen
Catholic University of Leuven, Leuven, Belgium
Andrzej Kuczumow
Lublin Catholic University, Lublin, Poland
I. INTRODUCTION
Moseleys law, formulated soon after the discovery of x-rays by Rontgen (Rontgen, 1896),
represented the direct and denite onset of the use of x-ray spectrometry in chemistry. The
rst successful period was completed in the beginning of the 1920s by creating order in the
periodic table of the elements and by the discovery of the missing elements (Weebs and
Leicester, 1967). X-ray uorescence (XRF) spectrometry has some unique features so that
it became an irreplaceable tool for the analyst. Not may techniques had such a brilliant
start to their analytical careers!
gThe rst commercial instrument became available around 1940 and was derived
from the x-ray goniometer of a diraction instrument. A reasonable estimation of the
number of wavelength-dispersive (WDXRF) instruments working today is 15000, of
which some 20% are multichannel spectrometers. In addition, about 3000 instruments
working in this mode are attached to the electron microprobes, mainly in Japan. Some
3000 energy-dispersive (EDXRF) instruments are working independently, and some
15002000 others are attached to electron and other [e.g., proton (Uda et al., 1987,
Folkmann and Frederiksen, 1990)] microprobes; a few hundred instruments are con-
nected to synchrotrons as excitation sources. About 300 instruments are working now in
total reection (TRXRF) and several in grazing emission modes (Klockenkamper, 1997).
The average price of a new WDXPF instrument in 1998 is of the order of magnitude of
$250,000, $100,000 for EDXRF, and $200,000 for TRXRF (Claes et al., 1997) and this is
not expected to rise much in the coming years. The calculation of the total money in-
volved in the x-ray instrument market made hereafter was based on the 50% amortization
estimate per instrument. We consider in our account only these parts of Particle-induced
x-ray emission (PIXE), electron microscope, and synchrotron arrangements which can be
treated as x-ray attachments. An auxiliary market was created also around the main
equipment business, covering the spare parts, recent supplements, and service connected
with the maintenance. Then, the commercial value of the instruments running today may
be estimated at some US$4 billion (Markowicz and Van Grieken, 1986; Van Grieken
et al., 1986). An important body of scientic literature relates to x-ray spectrometry
Copyright 2002 Marcel Dekker, Inc.

(Markowicz and Van Grieken, 1986; van Grieken et al., 1986; Jenkins, 1984; de Vries,
1986; Klockenkamper, 1987; Kikkert, 1983; Potts and Webb, 1992; Torok et al., 1996,
Torok et al., 1998; Szaloki et al., 2000; Brill, 1996; Ellis et al., 1997 and Quiset, 1996).
Literature about essentially diraction and scattering problems can also be very useful for
the researchers working in the eld of XRF (Fewster, 1996).
About 10% of the WDXRF instruments are applied in geological research and
prospecting (sequential and simultaneous spectrometers). Most of the simultaneous in-
struments are installed in industry, and the sequential instruments are distributed over
industry, analytical laboratories, and research institutes at universities and public services.
X-ray uorescence spectrometry is unique in element analysis of inanimate matter:
In qualitative analysis, it has unrivaled selectivity for all elements between beryllium and
uranium and also for transuranium elements and an extremely wide dynamic range in
quantitative analysis (ppm to 100%). Although the plasma emission spectrometry [Direct
Current Plasma (DCP) or Inductively Coupled Plasma (ICP)], atomic absorption spec-
trometry (AAS), neutron activation analysis (NAA), and dierent kinds of mass spec-
trometry (MS) have lower or much lower detection limits, the wide dynamic range remains
a unique feature of XRF (over ve decades). Moreover, it possesses the scarce virtue
among spectral methodsthe upper useful limit reaches the concentration of several tens
of percent of the total concentration for the main component. The detection limits at the
ppm level without preconcentration and the limits of precision and accuracy that can be
obtained (connected, in turn, to sample homogeneity and counting statistics) determine
the boundaries of its application.
Earlier books describing the techniques are mentioned in the reference list (Compton
and Allison, 1935; Jenkins and De Vries, 1967; Birks, 1969; Dyson, 1973; Jenkins, 1974;
Bertin, 1975; Tertian and Claisse, 1982; Lachance and Claisse, 1995, Jenkins et al., 1995;
Buhrke et al., 1998the latter is a kind of a guide for sample preparation in XRF and
XRD, but is cited here, because the problem is very important and nontrivial). The
purpose here is to describe the basic principles that allow wavelength dispersion of x-rays
and to describe all the components of a spectrometer.
The phenomenon of x-ray uorescence is only a small part of a much wider problem
of the interaction of charged particles or photons with matter (Feldman and Mayer,
1986). Dierent kinds of secondary particles are then emitted (Fig. 1a). Various combi-
nations of exciting=emitted particles are possible, giving birth to dierent analytical
techniques, with the combination photons as exciting particles=emitted photons as a
base for the x-ray uorescence. The angles the trajectories of the exciting or emitted
particles create with the surface of the sample dene normal XRF and PIXE methods and
total reection versions: TXRF (Chapter 9) and TRPIXE (Vis and van Langevelde, 1991;
van Kan and Vis, 1996a, 1996b, 1997). In addition, for the x-ray uorescence, a grazing-
emission method can be mentioned (GEXRF) (Sasaki, 1990; Becker et al., 1983; de Bokx
and Urbach, 1995; Urbach and de Bokx, 1996; Tsuji et al., 1995; Perez and Sanchez,
1997) (Fig. 1b).
Insofar as the fundamental principles are concerned, we may recall the law of
Moseley (Moseley, 1913, 1914), which is the basis of the qualitative application of XRF:
r
p c
n kZ s 1
l
where n is the frequency (in Hz), c is the speed of light (in m=s), l is the wavelength (in m),
k is the constant for a given series, and s is the screening constant. The relationship
Figure 1 Phenomena accompanying the interaction of x-rays with matter: (a) different
applications for analytical purposes (abbreviations of methods coupled with the use of particular
phenomena are mentioned; (b) different versions according to the incidence and emergence angles
(Itotal reflection XRF or PIXE; IIgrazing emission XRF; IIIgrazing incidencegrazing
emission XRF).

between the wavelength of the lines belonging to the same spectral series and the atomic
number is illustrated by Figure 2.
For high-Z elements, the XRF spectra become more complex and full exploitation
for qualitative analysis of mixtures is not always simple. Practical unraveling of spectra is
dealt with in Chapter 4.
The intensity of any spectral line is proportional to the number of atoms emitting
photons of energies attributed to this line. However, a simple linear proportionality is not
the rule. From the concepts of mass attenuation coecients introduced in Chapter 1,
it should be clear that the intensity of an analyte line of one species is attenuated by atoms
of the same species and by any other atoms present in the matrix. Matrix refers to all
elements present in a sample except the analyte element. Attenuation by absorption re-
presents a rst complication compromising the proportionality.
If the matrix contains elements with absorption edges of slightly lower energy than
the energy of the characteristic line of the analyte, strong absorption can occur. On the one
hand, this results in further attenuation of the analyte line and, on the other hand, in
enhancement of the spectral line related to the said absorption edge of the other matrix
element. This phenomenon is known as secondary uorescence. The process may be re-
peated with respect to all matrix elements with an absorption edge with a lower energy
than the energy of a uorescence line emitted by another matrix element. Secondary and
higher-order uorescence is the major complication deteriorating the simple proportion-
ality between intensity and concentration.
In Figure 3, three typical kinds of relationship between the relative intensity (mea-
sured intensity divided by the intensity obtained for the pure element) and concentration
(expressed as weight fraction) are represented. Curve I is obtained when the analyte line
undergoes absorption only. If enhancement occurs, the analyte line intensity is higher than
expected from primary excitation only and the curve is situated above the diagonal.
A similar curve, however, can be obtained when the mass attenuation coecient of the
matrix is lower than the related coecient of the element for its own radiation, as shown in
the case for Fe in FeO (curve II). In a special case, the mutual relation between attenuation
Figure 2 Representation of Moseleys law of K and L spectral lines.

Figure 3 Absorption phenomena in a heavy matrix (curve I), in a light matrix (curve II), and in a
neural matrix (curve III).
and enhancement coecients may be balanced such that both eects cancel precisely and
then the diagonal is approximated (curve III).
The eects just discussed are all energy (wavelength) dependent. This means that any
calculations converting intensities into concentration should include the attenuation and
higher-order uorescence eects and also integrate over all energies present in the exciting
primary beam above the value of the absorption edge and over all uorescence lines. This
is an ab initio approach for conversion of intensities into concentration implemented by
several authors. We mention here the articles by Gillam and Heal (1952), Sherman (1954,
1955), Shiraiwa and Fujino (1966, 1967), who in the 1950s and the 1960s proposed suitable
equations. Sparks (1976) and Li-Xing (1984) implemented small corrections and rene-
ments concerning the details of these expressions, and de Boer (1990) and de Boer and
Brouwer (1990) gave solutions to some dicult exponential integrals related to the en-
hancement. Important contributions to the numerical side of quantitative XRF are due to
Fernandez (1989), Fernandez and Molinari (1990), Rousseau et al. (1996), and Mantler
(1984). The rst two authors prepared commercial, customer-oriented versions of the
numerical programs XRFPc and CiROU, CiLAC, CiLT, and CiREG, respectively, and
Mantler paved the way for the analyses of multilayers. It should be emphasized that
Fernandez solved the transport equations for x-ray beams, the very general and powerful
but dicult tool for the description of particle beams. Likewise, Gardner and Hawthorne
(1975) obtained similar results by Monte Carlo simulation of x-ray excitation. A specic
approach was presented by Dane et al. (1996). These authors solved the problem of
quantication in situations where either an incomplete data set is available or where a
reasonable assumption about composition and=or depth prole cannot be done. Then, the
idea of processing whole sets of solutions (populations or strings or generations) has been
introduced, instead of processing the particular concentration values in consecutive
iterations.
In the fundamental parameter methods, the incidence and takeo angles are the
important parameters. As a rule, they are kept constant during the traditional run of
the analysis. However, there have been signicant eorts to use the angle-resolved version
of x-ray XRF spectrometers for depth proling of the samples (Gries, 1992; Schmitt
et al., 1994).
For a complete treatment of equations deriving the line intensities in x-ray uor-
escence spectrum from the elemental sample composition, the reader referred is to
Chapter 5.
II. FUNDAMENTALS OF WAVELENGTH DISPERSION
The crystal monochromator is the heart of a wavelength-dispersive spectrometer. Wave-

length dispersion of electromagnetic radiation in the x-ray region cannot be performed, as
a rule, by normal gratings but only by diraction on crystals or, for the long-wavelength
regions, on multilayers. We briey explain the principles because the construction features
of the monochromator are directly derived from them.
Consider a monochromatic beam of x-rays of wavelength l with their electrical
vectors of equal amplitude in phase along any point of the direction of propagation.
Assume further that the beam is parallel and is incident on a crystal at an angle W between
a given crystal plane (and all the planes parallel to this rst) and the incident beam di-
rection. The beam is scattered and diracted rays of equal l result but interfering con-
structively only in those directions for which the phase relationship is conserved. This
happens at an angle W for scattered rays 1 and 2 (Fig. 4), for which the path dierence
ABC of ray 2 with ray 1 is equal to an integral number n of wavelengths. From Figure 4, it
is clear that AB BC d sin W d sin W nl or, according to Bragg and Bragg (1913),
who rst formulated this relation, written as
nl 2d sin W 2
where n denotes the number of wavelength dierences between the rays scattered by the
adjacent planes. Following the recommendation of the IUPAC (Freiser and Nancollas,
1987), n is the order of diraction. If n 1, the dierence is one wavelength and the
diraction is said to be of rst order. If n 2, the dierence is two wavelengths and the
diraction is second order, and so on.
All x-rays emitted at angles dierent than W cancel because they are out of phase and
destructive interference occurs. From Figure 4, one can note that in the Bragg scattering,
Figure 4 Derivation of the Braggs law. ABC is the path difference.

the incident and exit angles are equal and, in this sense, there is some analogy to mirror
reection in the classical optics. However, diraction is by no means equal to reection in
classical optics, because the diraction is a volume not a surface process. It is less ecient
(with a great loss of intensity) and is performed only under particular angular conditions;
that is, according to Braggs law. Full analogy between the reection of x-rays and the
reection of optical rays happens only at grazing incident angles (i.e., smaller than the
critical Snells angle). This is intrinsically a consequence of the refraction index, which is
slightly smaller than 1 for x-rays. There are continuous eorts to construct a real mirror
on the basis of multilayers, which would eciently reect x-rays under large incident
angles, at least for soft x-rays (Kearney et al., 1991).
Thus, the static condition for obtaining diraction of a monochromatic x-ray beam
in some direction in the volume surrounding the analyzing crystal is given. What happens
in the case of a polychromatic beam of x-rays? For a crystal, one set of planes is selected
(for dierent reasons) and d is constant. If only rst-order diraction is considered and
constructive interference must be realized for all l present in the incident beam, then W is
the only variable:
l constantsin W 2a
The signal arriving from the diraction angle W is detected by a detector placed on a
goniometer arm. The detector rotates around an axis through the macroscopic plane of the
analyzing crystal. For a source at a xed position, the detector rotates over an angle 2W.
The wavelength is calculated from constant 2d and sin W. Note that this holds only for
the rst-order diraction. If the second-order diraction is used, the wavelength is equal to
half of that value. The maximum wavelength lmax that can be diracted in the rst-order
diraction by a crystal is equal to 2d because sin W 1.
Because wavelength and energy are related, one more equations must be given, al-
lowing us to convert wavelengths into energy units:
12398:5
E 3
l
where the energy E is in electron volts (eV) and l is in angstroms (A). It is a common
practice that the units used by x-ray spectroscopists are still electron volts or kiloelectron
volts for energy and angstroms for wavelength. When joules and nanometers are used, as
required by the international rules, the numerical value of the conversion constant be-
comes 1.9864561016 (nm=J).
The presence of dierent wavelengths of dierent order on the same goniometer
position has a particular consequence for wavelength-dispersive spectrometry. For a given
position of the goniometer (and detector), one may have a rst-order wavelength, say
0.6 A, second-order diraction of l 0.3 A, third-order diraction of l 0.2 A, or values
of energy 20.66, 41.32, or 61.98 keV, respectively. Figures 5 and 6, reproduced from the
work of Arai (1987) demonstrate a practical situation and Table 1 reprints a fragment
from x-ray tables by Cauchois and Senemaud (1978). Similar compendia of spectral lines
and attenuation coecients are easily available (Birks, 1974), as a rule covering the range
of elements between lithium (Z 3) to plutonium (Z 94). Much more controversial are
the values of the mass attenuation coecients for low energies and for low-Z elements at
the same time (Henke et al. 1982, 1988). If necessary, one can have access to the calcu-
lation for even heavier elements (So et al., 1977). It is easy to understand the practical
value of such calculations for the analysis. However, it is much more dicult to estimate
the accuracy of numerical calculations for transuranium elements. To sort out x-rays with
Figure 5 Higher-order overlapping of L series x-rays of Cr, Fe, and Ni to Ka of carbon. (From
Arai, 1987.)
Figure 6 Overlapping of CKa by higher-order x-rays of Ni, Fe, and Cr. (From Arai, 1987.)
wavelengths belonging to dierent spectral orders, a pulse-amplitude selector or detector is

needed that can make the distinction between energy levels. A detector is a device of which
the principle can be most easily explained by assuming the particle character of electro-
magnetic radiation. This is one reason that the characteristic of the impacting photons is
often expressed in terms of energy, not wavelength.
Table 1 Fragment of Detailed Tables of X-ray Lines
Notation
l (uX) l (mA) Element Transition usuelle Ordre E (keV) n=R n=R1=2
1251.56 1254.19 42 Mo KMIV KbII5 2

1251.64(a) 1254.27 58 Ce KMIV KbII5 4
1252.192 1254.824 62 Sm KLII Ka2 4
1252.58 1255.21 73 Ta abs. LIII 1 9.8776 725.99 26.9441
1252.6 1255.2 90 Th LINIV 2
1252.82 1255.45 73 Ta LIIIOIV,V Lb5 1 9.8758 725.85 26.9416
1255.17 1257.81 73 Ta LIIINVI,VII Lb7 1 9.8573 724.49 26.9163
1255.43 1258.07 32 Ge KLII Ka2 1 9.8552 724.34 26.9135
1255.50 1258.14 69 Tm KLI 5
1256.60 1259.24 75 Re LIMII Lb4 1 9.8460 723.66 26.9010
1256.71 1259.35 73 Ta LIIIOIII 1 9.8452 723.60 26.8998
1257.1(a) 1259.7 71 Lu LIINI Lg4 1 9.842 723.4 26.8956
1257.12 1259.76 90 Th abs. LII 2
1257.66 1260.30 73 Ta LIIIOII 1 9.8377 723.05 26.8897
1258.74 1261.39 54 Xe KLII Ka2 3
1259.210 1261.856 68 Er KLIII Ka1 5
1259.8 1262.4 90 Th LIIPII,III 2
1260.30 1262.95 74 W LIMIII Lb3 1 9.8171 721.54 26.8615
1260.6 1263.2 90 Th LIIPI 2
1260.620(a) 1263.269 58 Ce KMIII Kb1 4
1261.15(a) 1263.80 64 Gd KMIV,V Kb5 5
1261.23 1263.88 73 Ta LIIIOI Lb7 1 9.8099 721.01 26.8516
1261.956 1264.608 42 Mo KMIII Kb1 2
1262.68 1265.33 90 Th LIIOIV Lg6 2
1263.086 1265.741 42 Mo KMII Kb3 2
1263.428(a) 1266.083 58 Ce KMII Kb3 4
1264.6 1267.3 74 W LIIINIII 1 9.784 719.1 26.8158
1264.99(a) 1267.65 70 Yb LIINIV Lg1 1 9.7807 718.86 26.8116
1265.0 1267.7 91 Pa LIINIV Lg1 2
1265.24(a) 1267.90 69 Tm LINIII Lg3 1 9.7788 718.72 26.8090
1268.520(s) 1271.186 92 U LIINI Lg5 2
1268.66 1271.33 90 Th LINIII Lg3 2
1268.68(a) 1271.35 68 Er LIOIV,V 1 9.7523 716.77 26.7726
1270.2 1272.9 74 W LIIMV 1 9.741 715.9 26.7566
1270.35(a) 1273.02 64 Gd KMIII Kb1 5
Source: From Cauchois and Senemaud, 1978.
The dierences between wavelength-dispersive (WD) and energy-dispersive (ED)

XRF are due not only to the dierent detectors but also to other factors:
1. The brightness of a WD spectrometer is very low, the attenuation in a crystal
being responsible for an important part of losses. This problem may be
overcome by the use of radiation sources of signicant intensity, the synchrotron
being the best known but bound to the availability of this large facility.
2. The crystal is only the dispersive device, not the detecting device. The situation is
dierent in EDXRF, for which detectors play a double role: as the dispersive
device and as the detector at the same time.
3. Because Braggs law is geometric in character, the angular conditions for the
collimation of primary and secondary beams are very severe for WDXRF (8
25 msr), not the same as for EDXRF (150 msr) (Wollman et al., 1997). This
restriction on the geometrical eciency still makes the overall photon collection
eciency of a wavelength-dispersive spectrometer worse.
4. An attractive aspect of EDXRF is the simultaneous collection of the whole
spectrum, whereas a typical WDXRF device is exclusively sequential.
However, the maximum count rate for an EDXRF instrument is 30 kcps
for the whole spectrum, which severely limits the total number of accumulated
counts and, consequently, limits the precision (counting statistics). Similarly,
the limitation on the total count rate leaves a small margin for trace element
analysis. From the assumption, the trace element, if present in a sample, can
emit only a very small part of the total radiation emitted by a whole sample
(and there is also the background, participating in the total amount of
counts).
Simultaneous WD instruments are composed of a series of individual crystal spectrometer
(channels) operating simultaneously, but the number of channels is limited.
A comparison of wavelength- and energy-dispersive versions of x-ray spectrometers
is performed in a recent publication by Brill (1996).
III. LAYOUT OF A SPECTROMETER
The main parts of a spectrometer can be represented in the simplest form by Figure 7. The
analyzing crystal is the central point of the wavelength-dispersive instrument. On the left-
hand side of the crystal, we nd (1) the source of excitation, (2) the lters and devices for
shaping the exciting radiation (collimators and masks), and (3) the sample. On the right-
hand side, we nd (4) devices for shaping the diracted beam (collimators) and (5) the
detector. Signals from the detector are fed into the electronic circuitry where they are
shaped to be processed by the computer software for data analysis. This arrangement can
be reduced or made more complicated according to the demand. However, all possible
reductions lead to less exible devices, and complication does not necessarily enhance the
quality of the instrument.
Figure 7 A wavelength-dispersive spectrometer: FC proportional flow counter; SD scintilla-

tion detector. (Reprinted with permission of Siemens AG.)

A. Sources
A variety of radiation sources, emitting either charged particles or g- or x-rays of sucient
energy, are used for excitation of some or all elements of the periodic table and some or
most of the spectral lines of analytical interest. Other chapters deal with excitation by
protons [proton-induced or sometimes particle-induced x-ray emission (PIXE) (Chapter
12)], by electrons [electron microprobe (Chapter 13)], or by x-rays emitted from secondary
targets or from a synchrotron (Chapter 8). Excitation by x-rays or soft g-rays from
radioisotopes and x-rays from low-power tubes is mainly restricted to energy-dispersive
spectrometers (Chapter 3). The ideal excitation source would be a tunable x-ray laser
(monochromatic and intense, allowing the best choice of exciting wavelength and often
selective excitation), but this cannot be expected in the near future. Nevertheless, it is
worth reading some treatises about recent and future progress in the eld (Nagel, 1982;
Jamelot, 1995; Fill, 1995; Crasemann, 1994; London, 1993). There are serious reasons for
the slow progress in x-ray laser construction. The primary reason is that the population
inversion of electrons means a much larger deviation from the energetical equilibrium if
done between the levels, allowing the emission of x-rays. Consequently, it demands an
excessive pumping power, turning the pumped matter into a plasma. One must be aware
that the x-ray laser would be even much more useful in the elds of x-ray microscopy,
holography, litography, or for the research of time-resolved phenomena than as a source
for XRF analysis on a routine basis.
The synchrotron is another modern source of x-ray radiation, but it cannot be
considered as a tabletop instrument and a device for easy, inexpensive, and routine-based
applications. From a practical point of view, vacuum x-ray tubes are the overwhelming
choice among other potential excitation sources. High-power tubes are the only ones dealt
with in detail in this chapter; low-power tubes are discussed in Chapter 3.
All modern tubes owe their existence to Coolidges hot-cathode x-ray tube as pre-
sented in Physical Review some 85 years ago (Coolidge, 1913). They essentially consist of
a sealed glass tube containing a hot tungsten lament for the production of electrons, a
cooled anode, and a beryllium window. From a variety of modications proposed over
more than three-quarters of the century, two geometries have emerged as the most sui-
table for all practical purposes [the end-window tube (EWT) and the side-window tube
(SWT)], but now the preponderance of the EWT pushes the SWT out of the market.
Perhaps, a future deeper orientation of the WDXRF toward the microprobe applications
will renew the interest in SWT, which is much better in deriving parallel x-ray beams.
The general requirements of the x-ray tube as a source are as follows:
1. Sucient photon ux over a wide spectral range, with increasing emphasis on
the intensity of the long-wavelength tail of the white spectrum. The actual vivid
interest in low-Z element analysis will certainly activate research in this
direction.
2. Good stability of the photon ux (< 0.1% at least). Long-term stability reduces
the frequency of recalibration in routine analyses; short-term stability is an
absolute requirement for obtaining an acceptable precision.
3. Switchable tube potential (10100 kV), allowing the creation of the most
eective excitation conditions for each element. Still, in more high-power
constructions available on the market, putting a lter in the beam path is an
easier solution than switching the voltage (Shimadzu XRF-1700). For sure, the
selection of the spectral region for the targeted excitation by the use of a single
x-ray tube will never be as good as in dedicated synchrotron beam lines with
monochromators of the adequate quality, but the low cost of tube operation is
an obvious advantage. The intensity of the analyte lines varies considerably with
excitation conditions. An extreme example is given by Vrebos and Helsen
(1985a, 1985b) for simulated AlMo alloys.
4. Freedom from too many interfering lines from the characteristic spectrum of the
tube anode.
Freedom from interfering lines is important. The scattered characteristic lines of

the anode may spectroscopically interfere with analyte lines, disturbing the qualitative
recognition, the peak intensity estimation for the line of interest, and the accuracy of
subsequent conversion of intensity to concentration. This is found in the results obtained
after correction by some algorithms as well as by fundamental parameter calculations.
Although there is some kind of a remedy by the use of more ecient spectral decon-
volution methods (Remond et al., 1993; 1996), it occurs at the expense of a greatly
increased computational eort and depends heavily on the assumptions made a priori.
An x-ray tube is characterized by its anode element (a single element or two
elements as in dual-anode tubes), its input power [expressed in watts (W) or kilowatts
(kW), typically between 0.2 and 5 kW for high-power tubes], the voltage range between
anode and cathode (10100 kV for a SWT; limited to 60 kV for an EWT for the ma-
jority of commercial instruments), tube current [milliampere (mA), typically up to
60 mA or sometimes to 150 mA for high-power tubes], and an open (SWT) or closed
(EWT) anode cooling circuit. The photon output of the tube or, more importantly, the
photon ux hitting the sample (expressed in counts per second per watt of input power)
is determined by a, the incidence angle of an electron beam on the anode, the takeo
angle b (for SWT), the distance t to the beryllium window, the thickness d of the
beryllium window, and the distance between window and sample, t0 (Fig. 8). The ra-
diation output power is rather poor with respect to the input power and is of the order
of 1%, making the device a very inecient transformer of electron current to electro-
magnetic radiation. For an energy balance, see Bertin (1975) and some remarks by
Wollman et al. (1997).
The impact of the electrons creates an excitation volume from which the white and
the characteristic radiation of the target escape. This phenomenon represents the rst
distinct dierence between a SWT and an EWT. As shown in Figure 9a, the escape path
of the photons in SWT geometry is, on average, less than in the EWT geometry. An
immediate consequence of this characteristic is that dual anodes are used only in a SWT,
where a light element (e.g., scandium) covers a heavier element (e.g., molybdenum). By
switching the excitation voltage, x-rays are produced either in the upper (lighter) element
layer or in the substrate (higher-Z element), resulting in two distinct tube spectra with
dierent yields in the low- and high-wavelength regions (Fig. 9b). The popular dual-target
tube arrangements are now Rh=Cr and Rh=W.
The smaller the distance t, the higher the output. A decrease of t to half of the
original value increases the intensity roughly by a factor of 4. However, the reduction of
t in the classical setup is limited. The smaller the value of t, the more intense the bom-
bardment by the electrons and subsequent heating of the window by the scattered elec-
trons (Fig. 8). In a SWT, this bombardment is rather intensive because both the anode and
the window are in this geometry at ground potential. In a EWT, to the contrary, the -
lament and the window are both at ground potential, and heating of the window is neg-
ligible. For an EWT, however, t can be reduced to a certain extent only because it faces the
anode at high potential (Fig. 10).
Figure 8 Details of the geometry of a side-window x-ray tube and sample.
1. Alternative Congurations
To overcome the absorption of the low-wavelength tail of the continuum, a windowless
conguration was considered. This is an obvious solution, but it requires that the whole
spectrometer with sample, collimators, crystals, and ow counter be evacuated to the low
pressure suitable for securing an acceptably long life for the tube lament and conducting
analyses in the required range of the soft x-rays.
Nordfors (1956) advocated a dual-anode tube with two anodes physically separated.
They were excited by deviating the electron beam to either of the two anodes (Fig. 11).
Lack of stability prevented this solution from gaining commercial interest. Probably, a
modied version of this idea was introduced in the series 2000 x-ray spectrometers of
Diano (dual target dual lament; see Section VI).
Tubes with exchangeable anodes are another possibility for solving the problem of
comfortable switching between dierent anodes. To the best of our knowledge, this
solution is not commercially available because of the tedious exchange operation and
diculties in rigorous repeating of previous conditions of the tube action.
Using the sample as an anode is another solution, but then the application is
bound to conducting materials. In a modied form, this solution is implemented in
scanning electron microprobes. Because this anode cannot be adequately cooled, the
input power must be restricted to very low values, entailing low count rates and,
consequently, reducing the precision that can be obtained within reasonable counting
times.
Another possibility is to apply an existing 18-kW rotating anode x-ray tube gene-
rator. Sucient intensity is obtained. Part of this gain can be sacriced and Boehme (1987)
and Nichols et al. (1987) introduced the microdiraction beam collimator into the beam
Figure 9 (a) Principle of excitation in a side-window tube. (b) Principle of excitation in a dual-
anode x-ray tube (side window); Mo, W, or Au (for A) and Sc, Rh, or Cr (for B) are commercially
available anode components. The spectral feature of the tube spectrum depends on the energy of the
incident electrons.
derived from such a high-power tube. This collimates the beam to about 30 mm and allows
microuorescence. Squeezing the beam to more or less the same diameter is possible when
applying the polycapillary lens, even more so with the single capillary. These solutions are
very restrictive for the beam intensity; thus, a reasonable device conguration includes an
energy-dispersive detector instead.
2. Optimization
Because the takeo angle is a very important parameter, the surface of the anode can be
formed in steps in such a way that the yield of low-wavelength radiation is optimized. As is
clear from Figure 12, the step-shaped surface decreases the escape depths.
In a conventional EWT, the reduction of the anode to window distance t is limited
(Fig. 10). According to an old idea of Thordarson (1939), Botden et al. (1952) developed
an x-ray tube with a gold anode evaporated directly on the beryllium window. The tube
was used for surface radiotherapy. After many years, Phillips returned to Botdens
construction and again reduced t to zero by sputtering the anode target element directly
on the beryllium window (Fig. 13). In a SWT, the anode is at ground potential, which
Figure 10 Principle of end-window x-ray tubes.
Figure 11 X-ray tube with two separate anodes: (1) anodes: (2) filaments; (3) cooling;
(4) separating brass wall; (5) insulator. (After Norfords, 1956.)
Figure 12 X-ray tube with stepwise configuration of the anode.
considerably facilitates and simplies the safety requirements. This geometry enhances
the intensity by an order of magnitude, allowing a much lower input power: 200 W for
an intensity equivalent to the earlier 3-kW EWT. As a result of the low input power, the
heat produced in the target by the electron beam is easily dissipated and no supple-
mentary water cooling is required. The tube construction is reduced and only the most
basic components are left. The commercial name for this development is T3 or TTT
(target transmission tube; Fig. 14c). It is used exclusively in simultaneous WDXRF
instruments, especially in the new version of the PW1660 (Philips Technical Materials
Simultaneous X-Ray Spectrometer System PW 1660) (see Section VI).
Figure 13 Anode elements deposited on the beryllium window.
3. End-WindowTube
The essential parts of an EWT are displayed in Figure 14a. The ring-shaped cathode and
the cooling circuit of the anode are typical features of EWT construction. The latter
consists of a closed circuit lled with deionized water. Deionized water is necessary to
reduce the conductivity and enhance the safety because the circuit is at anode potential!
Electrons are diverted to the anode surface by electron-optics elements. Because the la-
ment and window are at equal potential, no electrons hit the window. Heating is mainly by
radiation from the anode, and an external cooling circuit is provided, which may be
connected to normal water supplies because it is not in contact with a voltage source.
Although the construction just described is in a common use now, it cannot be
considered as an ideal source of x-rays. Recently, van Sprang and Bekkers (1998) and
Kuczumow et al. (2000) have discussed the deviations from the homogeneity in the end-
window x-ray tube output. The geometry of the excitation system, as described by an
angle supported on the tube axis the sample point the goniometer entrance axis,
deviates from the formal geometry (about 83 ). The real, not formal, geometry of the
device can be read out from the shift in the Compton-scatter energy. It creates the
special demands for all the constructors of microprobes and milliprobes. They must
avoid using the conventional end-window tube. There are also the consequences for the
normal analysis: The uniformity of the samples and spinning operation are essential for
getting reproducible results. Otherwise, particular spots on a surface of the sample can
be irradiated in a dierent manner.
4. Side-WindowTube
An expanded view of a SWT is shown in Figure 14b. The essential dierences from an
EWT are the distance between cathode and anode, an earthed anode, and a single cooling
circuit for the anode only. This circuit may be directly connected to the normal water
supply because it is at ground potential. The geometric arrangement of the cathode
supports higher potentials of the cathode with respect to the anode. This is the basic
reason that tube potentials of 100 kV are allowed. Side-window tubes with ne-focus
anodes are used in many microprobe constructions. They are appreciated for their photon
output, easy to transform into a parallel, collimated beam. A consequence of the regulated
anode potentials is the possibility of use of dual anodes. The available dual-anode tubes
are summarized later in Table 10.
5. Tubes with Rotating Anode

The electrical input in an x-ray generator is high; however, a nal output of about 1% of
primary power is not very impressive. This must be due to the low eciency of conversion
of the electrical energy into the energy of x-ray photons. One should remember that
photon losses are even much greater in further parts of the spectrometer (especially
Figure 14 Different types of construction of commercial x-ray tubes: (a) end-window tube (EWT)
(courtesy of Siemens AG); (b) side-window tube (SWT) (courtesy of Philips Analytical); (c) target
transmission tube (TTT) (courtesy of Philips Analytical); (d) tube with a rotating anode (Vekemans
2000 courtesy of B. Vekemans).

Figure 14 Continued
in collimators and crystals). The desparate need for more ecient excitation sources
emerges with many more subtle applications of x-rays: the microprobe constructions,
(micro)diraction experiments with organic or biochemical materials, research on the ne
structure of the absorption edge, focusing of x-rays, or the application of the total
reection, for example. If one does not have access to the synchrotron, no patience to wait
for the beam time or no money for paying great sums for simple analyses, then the tube
with a rotating anode seems to be the best solution.
Figure 14 Continued
According to our knowledge, three companies, Rigaku, Siemens, and Enraf-Nonius,

constructed high-power tubes with a rotating anode. The anode, in the shape of a wide
cylinder placed on a narrower cylindrical rotary shaft, can rotate with a speed of 100 rps.
Mo, Cu, and Ag are the materials most frequently applied for the construction of the
anodes. The sides of the anode are under intensive electron bombardment, but the high
heat load is dissipated by the intensive rotation coupled with cooling by water, owing
inside the anode with a rate of 815 L=min. The system is evacuated by a prevacuum oil-
rotary pump followed by a turbo-molecular pump. It enables one to work with a voltage
of 60 kV and a current of 300 mA, sometimes even greater. It gives a power of the order of
2030 kW. Recently, the most powerful generator available is the Ru-1500 by Rigaku with
a 90-kW load. The application of power of the order of 2030 kW means roughly a 10-fold
increase in the intensity as compared to the conventional x-ray tubes. When coupled with a
Kumakhov lens, rotating anode tubes can be used as a powerful microfocusing source.
6. Compact Flash X-Ray Sources

An x-ray tube is a very conventional x-ray source, dating back to the times of Rontgen and
Coolidge. The eorts described earlier aimed at a better and more ecient construction of
the x-ray tube. Dierent versions of the tube were by no means the only solution for
constructing a better and more convenient source. The most pronounced progress of the
last decades is the synchrotron, but it is still far from an ideal device in terms of price and
size. Much more promising for most XRF laboratories seems to be a compact ash x-ray
source (Germer, 1979). Such sources are now being developed intensively, giving, for
example, a ux of photons with energies between a few kiloelectron volts to 200 keV, in
pulses lasting between 10 and 50 ns, with a repetition frequency up to 50 Hz. Doses are
very intensive, up to several roentgens per shot (Pouvesle et al., 1996). Primary x-rays from
such sources can be used for the excitation of x-ray uorescence, being especially useful for
real-time monitoring of kinetics of fast processes in ballistics and in the simulation of
accidents. It seems that the polycapillary x-ray focusing waveguide would be an ideal
supplement to this kind of x-ray source, giving the impetus for the development of a new
generation of pulse x-ray spectrometer. This device would combine the time resolution of
the source with the spatial resolution of the focusing polycapillary semilens.
7. High-Voltage Generator
A high-voltage generator supplying up to 60 kV for an EWT or up to 100 kV for a SWT
and an output power of 34 kW (or much lower, 0.2 kW for TTT tubes) is required. A
special generator is needed if one wants the high-power rotating anode tube. The con-
ventional power supplies were very cumbersome because of the size of the transformer.
The new generation belongs to the so-called switched power supplies. Such a power supply
is basically a dc=dc converter in which a dc voltage is electronically switched at high
frequencies (several kilohertz) and fed into an inductancecapacitance network. The
output power is not continuously regulated but is controlled through pulse-width mod-
ulation. One possible scheme of a switched power supply is given in Figure 15. The mains
are rectied (a), high-frequency switched (b), transformed (c), and rectied and smoothed
(d). The output voltage is sensed (e) and compared to a reference voltage (f), and this
signal monitors the pulse-width modulator (g), which, in turn, commands the switching
circuit (b). In the high-frequency transformer, a ferrite core is used; this is a lightweight
component. The whole setup allows the size of the generator to be reduced to a fraction of
the volume of classical generators.
The whole system is generally monitored by microprocessor. Power switching of the
tube is done preferentially along the isowatt curve (constant input power), all under
microprocessor control. The system has a number of safety switches on ow and tem-
perature controllers of cooling water with microswitches on all panels, which when
Figure 15 Principle of switched power supply: dc=dc convertor.

removed could expose the customer either to the electrical circuitry (high voltage of the
tube supply or the mains voltage) or to unacceptable radiation levels.
B. X-ray Tube Spectrum

The rst attempts to propose a quantitative description of the tube intensity as a function
of wavelength were made by Kulenkamp (1922) and Kramers (1923). The quantitative
treatment of intensities of uorescent x-rays (obtained by polychromatic excitation) by
fundamental parameter programs requires knowledge of the intensity function of the
exciting beam. This explains the continuous interest in the rigorous functional or nu-
merical description of the tube spectrum.
The description of the tube spectrum is divided into two parts, the rst concerning
the continuum spectrum [bremsstrahlung; see Seltzer and Berger (1985)] and the second
concerning the characteristic lines of the anode material superimposed on the con-
tinuum. The relative importance of these two contributions depends on the target ele-
ment: For a tungsten target, the characteristic L lines constitute the minority of the
emitted radiation, about 24%, and the K lines from the copper tube represent about
60% of the emitted radiation at 45 kV. The most popular Rh x-ray tube derives about
4% of the emitted x-rays as RhK and 20% as RhL photons; the rest is emitted as
bremsstrahlung (45 kV). The positive side of the latter tube is its relatively good output
of the low-energy photons, with a possibility of the excitation of the lines of heavier
elements by RhK lines.
In the continuum research, the main eort was focused on the accuracy of Kramers
law. Some deviations of this law from experimental results were corrected by the
introduction of a nonintegral exponent m in the wavelength-dependent term in Kramers
law (Brunetto and Riveros, 1984):

Zr l
Nl / 2 1 Kramers law 4a
l l0
m
Zr l
Nl / 2 1 Brunettos result 4b
l l0
where l0 is the wavelength at the short-wavelength (high energy) end of the continuum and
r and m are constants related to the power-dependent terms: atomic number Z and energy
function, respectively. The constants were determined by tting the theoretical curves to
the experimental results. Brunetto and Riveros result was conrmed later by Tertian and
Broll (Tertian and Broll, 1984). By no means does it exhaust the solutions; Many other
descriptions of bremsstrahlung spectra have also been published; to mention only the best
known, there are those by Rao-Sahib and Wittry (1972), Reed and Ware (1973), Fiori et al.
(1976), and Statham (1976a, 1976b). Finally, the reader can nd the interesting articles by
Small et al. (1987) and Trincavelli et al. (1998) summarizing the state of the art in this area.
Other corrections must be added to Eqs. (4): the absorption correction [often that of
Philibert; see Pella et al. (1985) and Markowicz and Van Grieken (1984)] and the ex-
ponential correction term including the absorption of the beryllium window.
Furthermore, in the article by Pella et al. (1986), an interesting algorithm was pro-
posed for taking the characteristic line intensities into account. For this purpose, these
authors made use of the equation proposed by Green and Cosslett (1961). The ratio of
peak to background intensity was found to be a function of overvoltage U0 and atomic
number Z:
" 2 #
Nchar U0 1 a U0 ln U0
exp 0:5 d 1 5
Ncon 1:17U0 3:2 b Z4 U0 1
Overvoltage U0 is the ratio of the initial electron energy E0 to the excitation energy of
a given shell Eex . The symbols a, b, and d are experimentally determined constants. The
intrinsic merit of this formula is its dependence on the physical parameter U0 and on Z [see
also the work by Murata and Shibahara (1981) with Monte Carlo estimations of the
penetration depth of electrons].
Recently, a series of papers on the numerical description of the tube output has been
published by Ebel et al. (1989) and Schomann et al. (1995, 1997). The solutions were
derived from the dierent depth distribution functions approximating the electron pene-
tration in anode materials.
Apart from all eorts concentrating on the numerical estimation of x-ray tube
emission, experimentally recorded spectra may always be used [collected in Gilfrich and
Birks (1968), Gilfrich et al. (1971), Gilfrich (1974), Brown et al. (1975), and Loomis and
Keith (1976)].
The same kind of calculation as for the spectral x-ray tube output is very helpful
for the description of the background in wavelength-dispersive XRF analysis. The
background is mainly determined by the scattered bremsstrahlung radiation from the
tube. The theoretical estimation of the continuous radiation should always be helpful
for solving background problems (Arai and Omote, 1988; Omote and Arai, 1989; Arai
and Shoji, 1990; Arai, 1991). Sometimes, the knowledge of background can be applied
for analytical aims (Kuczumow et al., 1992). In this case, a selected bremsstrahlung
channel provides quantitative (but not qualitative!) information about the sample
contents.
A similar approach has been applied in an article by Kuczumow et al. (1995) for the
extraction of the information included in the coherently scattered signal in the energy-
dispersive mode on the capillary version of x-ray spectrometry. A similar extraction of the
information from the Rayleigh signal in wavelength-dispersive XRF and from the selected
bremsstrahlung channel in the electron microprobe is possible as well (Kuczumow et al.,
1999). It concerns special samples (e.g., the biological ones) and the information obtained
is connected with the description of the matrix. It brings additional knowledge about the
density of matrix, which is sometimes of essential signicance in data evaluation. The
articles just mentioned described the analysis of tree rings and other similar periodic
structures, where the variability of the density of the matrix was, by far, more important
than the variability in the chemical composition.
C. Collimators and Masks

The wavelength-dispersive mode of operation depends strongly on rigorous geometric
constraints on goniometer construction and analyzing crystal. Ideally, only a parallel
beam of uorescence radiation should be diracted and stray radiation should be absent.
Stray radiation enhances the background. Diverging beams result in worsening of the
spectral resolution. Converging beams act in the same direction, but the latter are often
necessary for making microanalysis. If applied in such conditions, they demand a special
numerical treatment to obtain analytical results with a given level of condence. Useful
versions of fundamental parameter calculations for converging beams are now available
(Chang and Wittry, 1994).
Masks, which reduce the size of the uorescent beam in front of the collimator, cut
o x-rays emitted or scattered by an area larger than the sample area.
Three positions for collimators in the optical path of the spectrometer are possible:
(1) between the sample and the crystal, (2) between the crystal and the detector, and
sometimes (3) an auxiliary position between two detectors working in tandem. Collimators
are not the ideal devices because they deliver a divergent photon beam with the angle of
divergence a given by

a
a arctan 6
l
where a is the spacing between the blades and l is the length of the blades. In addition to
divergence, there is also a substantial loss of counts while passing the collimator; for ex-
ample, for a radiation of about 10 keV passing by a typical 10060.25 mm Soller colli-
mator, the transmission is close to 105. On the bonus side of the use of collimators, it
must be said that the resolution is improved very substantially (see Fig. 16). Thus, one
needs to nd a compromise between better resolution and higher brightness. In the deter-
mination of light elements, for which the intensity is relatively low (because poor excita-
tion and ecient attenuation) but relatively well-spaced spectral lines exist, the demand for
intensity prevails over resolution and, whenever possible, a coarse collimator (or none at
all) is usually sucient. Further considerations on this topic are in Section III.D.2. related
to multilayers. In all focusing spectrometers (with curved crystals), the use of collimators is
superuous and the role of collimators is taken over by pinholes or slits.
D. Dispersive Elements
Both the primary photon beam derived from the x-ray tube (or another source of radia-
tion) and the secondary or uorescence beam derived from the sample can be mono-
chromatized. The monochromatization of the primary beam is not essential but can be
made for more ecient excitation of the selected elements by photons of chosen wave-
lengths or for radical simplication of calculation procedures (the fundamental parameter
calculation is then transformed to simple LachanceTraillTertian correction). Mono-
chromatization may be compared to the action of a narrow bandpass lter by which only a
small band of the whole spectrum is transmitted. The width of the bandpass is related to
the spectral resolution. A number of parameters characterizes this process.
Figure 16 Two spectra from the same sample demonstrate how an auxilliary collimator reduces
line overlap when measuring heavy elements (a) without and (b) with auxillary collimator. (Courtesy
of Phillips Analytical. From Phillips Materials.)

The ratio DE=E, where DE denotes the energy width of transmitted radiation band
and E the energy of photons to be transmitted (the mean energy in case of a wide band), is
called the relative spectral resolution of the monochromator. DE is generally expressed as
full width at half-maximum (FWHM) of the transmitted band (a peak in intensityenergy
representation). The reciprocal of spectral resolution, E=DE, is called the resolving power.
The same can be expressed in wavelength units as Dl=l by transformation through Eq. (3).
Both expressions are numerically equivalent but of opposite sign. For the wavelength-
dispersive spectrometer, the angular dispersion (Braggs dispersion) is important and is
obtained by dierentiation of Braggs law:
dW n
7
dl 2d cos W
The monochromatization of the primary beam, if required, is made by the use of
lters or secondary targets. The absorption edges of the elements present in the lter
should be at lower wavelengths than the wavelength domain to be transmitted. Sec-
ondary targets emit their own characteristic radiation without a white background
(except the scattered part of the primary beam) and with a population density of peaks
depending on the atomic number of the secondary target. In both of these cases,
the monochromatization is far from being perfect. A relatively simple application of
double total reection from the quartz plates was proposed with success for mono-
chromatization in TXRF (Schwenke and Knoth, 1982). The criteria for the mono-
chromatization of the primary beam dier substantially, depending on the application.
They become very sharp in some methods of research [photoelectron spectroscopy, ex-
tended x-ray absorption ne structure (EXAFS)]. Then, the methods of mono-
chromatization of the beam are dierent also, depending very much on new discoveries
in x-ray and related optics. In general, the strong monochromatization of the beam is
associated with a great intensity loss and can be made for the very ecient sources of
x-rays as synchrotrons.
The eorts for the virtual numerical monochromatization of the real exciting beam
by the introduction of the so-called equivalent wavelength concept failed. A new
equivalent wavelength is needed for each analytical situation (e.g., change in composition).
The gain from the simplication of the spectrum is doubtful as compared with the great
increase in the numerical eort.
The monochromatization of the secondary beam is the key problem. Dispersion of
radiation is needed for the specic detection of characteristic lines. There are, however, a
number of analytical problems in which the requisite dispersion is low. In limited cases, it
may be sucient to subdivide the spectrum into two spectral windows, from which one is
to be detected. In other cases, the cutting o of a relatively wide spectral window may be
sucient, as is done in the Philips MiniMate device, where only a sealed gas proportional
counter is applied for the photon energy discrimination. In practice, this selection of wide
spectral domains is easily performed by energy-dispersive systems and pulse-height se-
lection, by lters or by a set of balanced lters. A spectrometer for general use over the
widest range of elements, however, should be equipped with monochromators of sucient
overall resolution, as is obtained by crystal diraction.
1. Crystals
According to the orientation to the possible crystallographic planes of the crystal, dierent
values for d are preferentially diracting and, coupled with it, a dierent resolution results
for a given wavelength. A few values has been calculated for LiF in dierent orientations
and these are listed in Table 2. From the dispersion, it can be expected that the Ka line of
manganese can be separated from the chromium Kb by LiF (220), not by LiF (200). The
values in Table 2 are calculated for ideal crystals and a parallel beam. For real crystals, the
dispersion and resolving power are less favorable; some real values for a complete spec-
trometer are provided later. In Table 3, a list is presented for crystals currently available
for spectrometers: lithium uoride (LiF), silicon (Si), germanium (Ge), pyrolytic graphite
(PG), indium antimonide (InSb), pentaerythritol (PE or PET), ethylenediamine-d-tartrate
(EDDT), ammonium dihydrogen phosphate (ADP), thallium hydrogen phosphate
(TlAP), and multilayers with their commercial designations. Important characteristics
other than the interplanar distances codetermine the ultimate usefulness of an analyzing
crystal: spectral resolution, mosaicity, reectivity, stability, the thermal expansion coe-
cient, and the spectral range.
a. Resolution
The spectral resolution DE=E of the crystals oscillates about the value 102, with few
exceptions. The data for the resolution of dierent crystals are included later in
Figure 26a, a summarizing gure on resolution [see also Kuczumow and Helsen (1989)].
The spectral resolution for the crystals is, generally speaking, better than that of other
dispersive devices, such as detectors or lters, but the dierence with respect to the
energy-dispersive spectrometers becomes less favorable for the short wavelengths. The
progress in superconducting tunnel junctions detectors (Finkbeiner et al., 1991; De
Korte, 1992; Le Grand et al., 1993) and microcalorimeter detectors (Lessyna et al., 1993;
McCammon et al., 1993; Silver et al., 1996) during the last decade shows that these
devices would have even better spectral resolution in the medium energy range (i.e.,
above 45 keV) than the crystals (see Fig. 26b). However, it is a question of compromise
among price, necessity to work at liquid-helium temperatures, the very value of spectral
resolution necessary for a given analysis, and the loss of intensity in crystals on one
hand and the poor count rates allowed in the newest detectors on the other hand, which
decides what kind of resolving device will be the future choice for commercial appli-
cations.
b. Mosaicity and Reectivity
Real crystals have all kinds of imperfections, and mosaicity is one of them. Mosaicity
refers to the existence of blocks within the crystal with sizes of the order of magnitude
of 100 A, which have slightly dierent orientations and lead to widening the diracted
peaks. This happens to widely diering degress: topaz, EDDT, ADP, and gypsum exhibit
low mosaicity, quartz and LiF a little higher mosaicity, and PET a signicantly higher
Table 2 LiF: d Spacings for Different Orientations and Angular

Dispersion
Crystal 2d (A) Dispersion
LiF (422) 1.652

LiF (420) 1.800
LiF (220) 2.848 0.5154
LiF (200) 4.027 0.2902
Note: Calculated for W angles corresponding to MnKa (2.102 A) and n 1.

Table 3 Currently Available Crystals
Crystal 2d (nm) Element range Remarks
LiF(420) 0.180 NiU High resolution, special applications for

heavy-element K lines
LiF(220)a 0.2848 VU High resolution, good intensity
LiF(200)a 0.4027 KU General purpose, wide range, best diffracted
intensity
Si(111) 0.6271 P, S, Cl Supresses even orders
Ge(111)a,b 0.6532 P, S, Cl Supresses even orders, good for
intermediate- and low-Z elements
PG(002)a 0.6708 P, S, Cl Good intensity, poor resolution
InSb(111)a,b 0.784 Si
PET(002)b 0.8742 AlCl Good intensity, low spectral contamination,
soft
EDDT(020) 0.8808 AlCl Lower intensity than PET, problems with
stability
ADP(101) 1.064 Mg Still lower intensity
TIAP(100) 2.575 OMg Especially F, Na, Mg, poisonous
PbSt 10.0 F, C Good resolution, low intensity
LTC 15.6 Up to Be Longest wavelengths known for
semicrystals structures
PX-1a 4.93 OMg Low resolution, good intensity
PX-3a 19.5 B Low resolution, good intensity
PX-4a 12.2 C Low resolution, good intensity
OVO 55 5.5 Mg, Na, F Low resolution, good intensity
OVO 100 10.0 C, O Low resolution, good intensity
OVO 160 16.0 B, C Low resolution, good intensity
OVO H300 30.0 Be, B One of the largest 2d available up to now
PX6
a
Also available as curved in simultaneous instruments.
b
Also available as transversely curved for sequential instruments.
mosaicity. A result is a slight angular widening of the diracted peak on one hand, but on
the other hand, the intensity of the peak is generally enhanced. Widening is smaller than
widening due to other geometric factors of the whole spectrometer and the loss can be
tolerated while compensated by the increase in intensity. Some mechanical treatments
enhance the mosaicity, and LiF crystals are easily improved in that way. The angular
intensity distribution of a diracted peak, the rocking curve, can be determined by double-
crystal spectrometer. In Figure 17, the peak height of the represented curve obtained by a
high-resolution spectrometer is determined by atomic scatter factors and the space group
of the analyzing crystal, whereas the width at half-maximum is determined by the mo-
saicity of the analyzing crystal and the divergence of the incident and diracted beams.
The surface under the curve is the integral reection or, when the curve is normalized to
the intensity of the incident beam, the integral reection coecient. This coecient is very
much dependent on mosaicity. Abraded LiF has a 10-fold increase in the reection
coecient compared to freshly cleaved LiF (36105 to 46104 rad), measured by using
CuKa radiation (Birks, 1969). LiF crystals have also the great advantage of low ab-
sorption by their constituting atoms. Topaz and quartz, otherwise good crystals, have
Figure 17 Rocking curve that would be obtained from a real crystal-diffracting parallel
monochromatic radiation (rocking curves are actually measured on double-crystal spectrometers):
P the peak diffraction coefficient; R the integral reflection coefficient. (From Birks, 1969.)
poor reectivity properties, whereas PET is very good in this respect. Reection constants
as a function of wavelength are given in Figure 18.
c. Stability and Temperature
The mechanical stability of most crystals is satisfactory, but there are exceptions. Gypsum
can eoresce (especially in a high vacuum); PET has a tendency to change phases on aging
Figure18 Single-crystal integral reflection coefficients of graphite, LiF (200), LiF (220), and KAP.
[From Gilfrich et al., 1971). Reprinted by permission of Analytical Chemistry. Copyright #
American Chemical Society.]

and it is soft so that it is easily damaged when manipulated. The temperature inside the
measuring chamber of a spectrometer is kept as constant as necessary (< 1 or < 0.01 C if
chemical peak shifts have to be measured). In these circumstances, damage of the organic
crystals by high temperature is not likely to occur. When very precise measurements of
peak position are to be made for speciation purposes, the thermal-expansion coecient is
important. PET is very disadvantageous in this respect; topaz is in the opposite situation.
It should be noted that the characteristic spectral lines of the crystal can be super-
imposed on the spectrum, making it obscure or even unt to use, especially when it
suggests the presence of some elements in a false way. Crystals of excellent resolving
features, Be and Ge (111), have their own lines in the soft x-ray region.
d. Spectral Range
The useful spectral range covered by one crystal is limited. The maximum wavelength is of
trigonometric origin and is imposed by Braggs law, namely by the condition that sin W < 1
and lmax < 2d. In practice, the goniometer is scanned for values of 2W varying from a few
degrees to about 150 . However, for higher values of 2W, an angular dispersion widens the
peak proles. On the contrary, in the low-2W range, only a small fraction of x-rays emitted
by the sample is intercepted unless the analyzing crystal is very long. The surface of the
crystal projected on a plane perpendicular to the x-ray beam may be smaller than the
width of the beam emerging from the collimator. Thus, 2W values as well as the macro-
scopic dimension determine the useful spectral range of a crystal.
For x-rays of low energies, the interplanar distances of real crystals become too
small. Some substances, namely salts of heavy metals with organic acids with long chains
(otherwise the soaps of heavy metals), can take over the role of dispersive structures if their
organic chains are regularly arranged. There are special techniques for making such
quasicrystals. The individual layers are called LangmuirBlodgett lms. The ends of hy-
drophobic chains of adjacent layers join each other, and the heavy metal ends are con-
nected to the next heavy-atom ends from the next molecules. Many features of such lms
depend on the length of the chain. A great number of similar structures with a wide variety
of interplanar distances 2d (up to 156 A in the case of lead melissate) have been synthe-
sized. LangmuirBlodgett structures have dierent negative properties: for example, they
are soft and not very stable, strongly hydrophobic, and of low reectivity. Some of them,
like thallium adipate, are highly poisonous substances.
e. Curved Crystals and Other Focusing Systems
Not only are at crystals used in the goniometer. Some focusing systems, such as the
Johann, Johansson, and Cauchois arrangements, may be used (Fig. 19). Then, the crystal
must be curved, with the curvature radius equal to the diameter of the Rowland circle and,
at the same time, to the Bragg curvature, being half that of the Rowland circle. Three-
dimensional crystals can sometimes meet both of these conditions. The focusing arrange-
ments are extremely useful in all cases in which the sample area is small, losses of intensity
are prohibitive, and scanning over large angles is not necessary. In these arrangements,
x-rays are collected in one point by focusing on the detector. An obvious virtue of such an
arrangement is found in the analysis of small sample areas and by a using focused exciting
beam, as in electron or proton microprobes. In such situations, the curved crystal geometry
allows the collection of x-rays from a relatively large solid angle of diverging x-rays to a
small spot (Fig. 20). A consequence is that the collimators normally placed between the
sample and the crystal, and the crystal and the detector must be replaced by slits and
pinholes. The focusing geometry is a very economical arrangement for saving intensity (the
brightness of such a device is estimated to be up to two orders of magnitude greater than
Figure19 Curved crystal x-ray arrangements in (a) Johann, (b) Cauchois (in transmission), and (c)
Johansson version. S entrance slit of radiation; D exit slit of diffracted radiation; d crystal
lattice spacing.
Figure 20 Focusing of x-rays by a logarithmically curved crystal. (Courtesy of Siemens AG.)
that of conventional at geometry). The curved crystal geometry is applied in simultaneous

instruments in which scanning is not used and an optimized arrangement is chosen for each
wavelength (element) implemented. Then, logarithmically curved crystals are used. In a
new version of the sequential instrument (Venus), Philips used the reverted channels taken
from the simultaneous instrument. Crystals applied in that construction are curved as in a
simultaneous device and their position is additionally adjusted by a screw to trap as much
intensity as possible. In general, during the last two decades, great progress took place in
the planning and construction of the optical elements based on curved reecting or dif-
fracting surfaces of crystals and multilayers; most of the developments were in the syn-
chrotron version of x-ray spectroscopy (Ice and Sparks, 1984).
The curved crystal version of the x-ray microprobe is not the only known solution. The
progress in x-ray optics during last decades enabled the easy concentration of x-rays while
being transmitted through a single capillary (Rindby, 1986; Carpenter 1989; Thiel et al.,
1989) or even through a semilens based on the bundle of capillaries (Kumakhov and Ko-
marov, 1990; Yiming et al., 1994; Dagabov et al., 1995; Xunliang et al., 1995; X-Ray Optical
Systems Inc., 1997, 1998). This rst possibility, due to the great loss of intensity resulting
from a poor interception of the primary beam by the narrow inlet of a single capillary, is
limited to the energy-dispersive version of x-ray spectrometry (Attaelmanan et al., 1994).
The second version is more interesting from the point of view of WDXRF. A properly
curved capillary bundle can serve as a kind of semifocusing lens with a well-dened
Figure 21 Cross section of a typical multicapillary lens: (a) focusing configuration, from wide
spot (divergent source) to another spot (semifocus); (b) configuration transforming the divergent
into the parallel beam. (Courtesy of X-Ray Optical Systems Inc., Albany, NY. and personally from
Dr. J. P. Bly.)
curvature and moderately-dened focus (Fig. 21). The intensity of the beam leaving the
lens is, of course, lower than the intensity derived from the x-ray tube, but still sucient
for many applications. Moreover, the primary collimator is removed in this system and the
gain from this removal is partially balancing the loss resulting from the bundle construction
and operation. One can estimate the focal distance f of such a lens as
df d0 2 f ycr 8
where d is the spot size, d0 is the diameter of the capillary end, and ycr is the critical angle
of the total reection. As a rule, the polycapillary array is introduced to concentrate the
primary beam, but it can also be used for the collection of secondary x-rays outgoing from
the sample, before reaching the curved crystals in nonconventional arrangements.
2. Multilayers
The limitation of XRF analysis in the region of soft x-rays is one of the most serious
limitations of crystal monochromators, although none of the rst principles constituting
the background of XRF method puts this limitation explicitly. Moseleys law determines
the rules for qualitative analysis of any element except hydrogen and helium, and the
Shiraiwa and Fujino equations govern quantitative analysis. Irresolvable problems oc-
curred until the late eighties because of troublesome absorption, lack of an adequate
dispersive device, and bad detection while passing to longer wavelengths. The concept of
multilayers or, strictly speaking, layered synthetic microstructures (LSMs) or multilayer
interference mirrors (MIMs) solved at least part of the problems.
Two approaches to the idea of a suitable analyzing device in the soft x-ray domain
have been applied from the very beginning (Underwood and Barbee, 1981). The rst re-
sulted from consideration of Braggs equation [Eq. (2)]. This indicates that if any crystal of
a longer interplanar distance is found, it will be possible to disperse longer wavelengths in
the soft x-ray range. The potential candidates for long-period crystals or quasicrystals,
such as clay minerals of the chlorite (14 A) or illitemontmorillonite (2530 A) type, are
not suciently ordered in this respect (Weaver and Pollard, 1973). Unfortunately, natural
crystals, irrespective of their dierent crystallographic planes, oer only limited possibi-
lities in this spectral range; specically, their reectivity is very low. The class of structures
called LangmuirBlodgett lms was more promising, but the reectivity and thermal,
mechanical, and chemical stabilities were rather poor.
A correct solution resulted from generalization of Braggs law, namely that dif-
fraction also occurs in media consisting of layers of dierent refraction coecientsin
other words, in sites of dierent periodically changing electron densities. Such structures
may be formed in an articial way. They may be treated as crystallike substances ordered
along the c axis (i.e., spacing d or 2d), but with uncontrolled arrangement within the
ab plane. The structure in the ab plane can be amorphous, provided that the optical and
mechanical properties are uniform in these directions.
The rst eort of synthesis was made in 1940, but the AuCu multilayer of Du
Mond and Youtz (1940) did not survive more than a few days because of deterioration by
interdiusion. The problems of thermal, radiative, diusional, and chemical instabilities
of multilayers have recently been solved. Signicant progress in this eld has taken place
in the last three decades, hence some years before the application of multilayers in
WDXRF.
The second approach was the result of an increasing interest in x-ray optics. As a
branch of physics, x-ray optics is nearly as old as the discovery by Rontgen, but because of
the specic properties of x-rays, its progress has been slow. All existing substances exhibit
complex refractive indices:
m 1 d ib 9
where m is the refraction index, d is the so-called unit decreament, a real number, and the
imaginary term b is related to absorption. The refraction indices in the x-ray region are all
below but very close to 1. This makes all eorts of x-ray focusing by lenses in a traditional
sense an impractical task. Franks (1977) gives an example of a lens with a curvature radius
of 10 mm built of a material with d 5 105 . The focal length of this lens is 100 m. In
such a situation, only glancing, grazing, and diracting features of materials have been of
practical interest for a long time. Otherwise, the grazing optics conditions for x-rays are
extremely severe. However, the need for mirrors, monochromators, and focusing devices
for the x-ray region is increasing rapidly in the elds of synchrotron radiation, plasma
research and diagnostics, x-ray microscopy, x-ray uorescence analysis, diraction, thermo-
nuclear fusion, x-ray laser, x-ray astronomy, and even x-ray waveguides. The invention of
multilayers dened this time as a complex set of particular layers consisting of materials of
periodically dierent refractive indices gave great impetus to progress in this branch of
optics. Some important properties of the materials used to produce the multilayers are
discussed in the next section.
a. Nature of Materials
In principle, three kinds of material are necessary for the synthesis of multilayers. First,
there must be a support (sometimes called a substrate), such as a piece of at or curved
silica layer, with an ideally polished surface. This condition is very important because the
roughness of the surface is translated to the deposited layers, correctable almost ex-
clusively when one of the layers consists of amorphous materials such as carbon. After
years of progress in the eld, when the roughness of the interfaces have probably reached
the limit of about 2 A, the most important contribution in it is from the deviations of the
substrate from atness (Kortright, 1996). Two sources of relatively inexpensive and pre-
cisely polished supports were found: silicon wafers as used in microelectronics (curved)
and glass or fused-silica optical elements for low-scatter mirrors (at or curved). The
additional polishing is the last step in the preparation of the substrate for further manu-
facturing of the multilayer. An even more complicated role for the substrate is described
by Nicolosi et al. (1986) in whole coal analysis. The authors determined the contents of
C, N, O, and F using multilayered microstructure PX2 and the contents of P, S, K, and Ca
by taking advantage of diracting properties of the supporting wafer of silicon (111) on
which the multilayer was settled.
Heavy metals (Hf, Pb, W, Mo, Pt, Ir, Ru, Rh, Os, Ni, Co, Fe, and Cr) and light
elements or compounds [Al, B, B4C (Ovonic Synthetic Materials Co., 1987), BN, Be, C, Si,
SiO2, SiC, Ti and Scthe last with the high reection] may be used as materials for al-
ternating high and low optical densities, at the same time being strong and weak scatterers,
respectively. Sometimes, materials from the rst group are called absorbers, and those
belonging to the second group are called spacers. The reactive materials and substances
with a low melting point are excluded from the list. Both components of the multilayer
should not share a common crystalographic structure, to avoid the epitaxial growth. The
selection rule for the materials can easily be understood from Figure 22 for boron. The
mass attenuation coecients for the boron K line, as presented versus the atomic number
of the absorber, have several minima. One falls in the region of boron (weak self-ab-
sorption) and carbon, and the next very deep minimum is in the region of nio-
bium=molybdenum. It puts the constraints on the materials, which can be used for the
determination of boron. The rst, a low-density material, can be carbon or even better
B4C; the second, a high-density material, should be niobium or molybdenum. Indeed,
Philips made the structure PX3, composed of Mo=B4C, with a period of 195 A, adviced
for the determination of boron. However, when a new multilayer should be synthesized
Figure 22 Mass attenuation coefficient for the BKa line drawn against the possible absorbers in
the periodic table. Arrows show the deep minima in coefficient value. (Courtesy of Bruno Vrebos
inspiration.)

with high reectivity in mind, then the attention is put, instead, on a pair of materials with
a small value of the scattering DebyeWallner factor [see Eq. (10)]. Here, the W=B4C
tandem is a very good one. As a rule, the low-electron-density compounds are selected
from the elements with K absorption edges above the energy of spectral lines to be
measured. In that sense, boron and carbon are selected for multilayers of spacing above
50 A and beryllium and carbon for spacings above 120 A.
b. Smoothness
This parameter is of great importance on each level, starting from the supporting
substrate to the last upper layer. All rough places, uneven layers, disturbances in in-
terfaces, interdiusion, and chemical interaction regions or defects, act in a manner
analogous to the thermal motions in classical diraction analysis. During synthesis, the
extent of roughness can vary in a dierent manner: In some cases, it tends to
smoothness, in others to further growth. The use of amorphous materials to form some
layers favors smoothing. The greater interplanar distances are, the more pronounced
the roughness is. On the other hand, the smoothness probably has its limits, even in
the case of multilayers with relatively small interplanar distances, with the Debye
Wallner parameter s tending to reach a value of about 2 A. It probably results from
the smoothness level obtained during the substrate production. Finally, it puts some
domination of the DebyeWallner parameter over other possible factors inuencing the
quality of multilayers in the region where the interplanar distance is not very long (say,
a few tens of angstroms).
c. Reectivity and Thickness of a Multilayer

Classical dispersive crystals exhibit low reectivity in the soft x-ray range. The situation
was greatly improved in multilayer reectors in which a single layer at normal in-
cidence angles exhibits a reection coecient of the order of 104 rad. This coecient
is, however, proportional to the square of the electrical eld amplitude (i.e., to a value
of the order of 102 for the amplitude reection coecient). Thus, a multilayer con-
sisting of 100 single layers may provide almost the maximum reectivity if the ab-
sorption can be neglected (Underwood and Atwood, 1984; Underwood, 1986,
http:==www-cxro.lbl.gov==multilayer=survey.html, 1998). For long wavelengths, the re-
sults are not so impressive; for example, in the very important region of the so-called
water window (284530 eV), the reection coecient was lower than 3% (Kozhevnikov
et al., 1994). The region is of essential signicance for the construction of an x-ray
microscope based on zone plates for biological research (Kirz et al., 1995). These re-
sults are in accordance with the calculations by Rosenbluth concerning numbers of
layers necessary for saturation of reectivity [data cited by Barbee (1986)]. Peak
reectivities of some commercially available multilayers [e.g., Philips materials PX1,
PX2 and PX3 (Nicolosi et al., 1986; Van Eenbergen and Volbert, 1987) and the
OVONYX line of multilayers [(Ovonic Synthetic Materials Co., 1987)] are often
compared to classical pseudocrystal dispersive structures, like lead octodecanate and
thallium acid phthalate. The predominance of the multilayer structures over classical
structures is striking, and spectral resolution is the only parameter in which the classic
crystals are better (Van Eenbergen and Volbert, 1987; Henke et al., 1986). Still, when
using multilayers, one must remember the weak points inherently coupled with those
devices: great refraction eects (Martins and Urch, 1992; Luck et al., 1992), deviating
the eective 2d value of the structure from the real value by as much as 5%, and
poorly shaped background with ghost lines in some cases.
d. Quality of Layers and Boundaries
The structure of the multilayer ought to exhibit geometric features. This condition is very
strict. Thus, at layers or gured structures must be uniform, the latter with controlled
curvature, without defects but with clearly dened optical parameters. All deviations
from an ideal model, easy to estimate by the reectivity characteristics, are, as a rule,
coupled by the use of the DebyeWaller factor into the eective roughness parameter se,
including both thickness errors and imperfect boundaries (Spiller and Rosenbluth, 1986).
The DebyeWaller factor DW is the Gaussian-type term describing the reduction of re-
ected amplitude at a boundary:
" #
2ps cos a 2
DW exp 2 10
l
where s is the width of a smooth transition layer and a is the propagation angle of
electromagnetic radiation, measured from the normal to the boundary between a medium
with one refractive index to another.
The question arises, however, whether the errors result from a rapid or from a mild
change of the optical features on the boundaries. Any roughness of a given layer decreases
its reectivity (Payne and Clemens, 1993), but a random distribution of roughness may
bear higher reectivities of the higher-order peaks. Moreover, many other physical factors
can inuence the uniformity and expected layer characteristics: Both the support and the
particular monolayers can have dierent slopes, densities are subject to uctuations, the
elements can diuse, or some chemical elements can mutually react (e.g., W with C or Mo
with Si) (Rosen et al., 1993). It should be emphasized that despite of so many obstacles,
the magnitude of the roughness in such a totally articial structure can be kept in the range
of an atom radius (Barbee, 1986).
The numerical description of multilayers is based on the matrix method (a matrix
expresses the features of a layer or interlayer region, and for the characteristics of a
multilayer, the product of matrices is written) or on the recursive use of layerreection
transmission characteristics. Deviations of empirical results (mainly reectivity measure-
ments) from the model predictions are associated with roughness. In this case, se, the
roughness parameter, results from the best t of empirical data to the model.
The selection of an adequate method of synthesis and subsequent control of pro-
duction and quality is a key question. Many methods were checked, and the aim of all
these processes was the deposition in which one atom follows another. The physical vapor
condensation, chemical vapor deposition, electrochemical covering, and sequential ad-
sorption of lms are the most promising methods. However, for the time being, the rst
method prevails. Two basic versions of physical vapor deposition are usedwith thermal
and sputter sources. In the thermal source technique, the covering materials are evapo-
rated by electron beam or laser evaporation. The vapor source and samples are in a xed
position. The time of evaporation is a parameter controlled by shutters or by pulsed laser
irradiation. An in situ monitoring system was used as a feedback system for controlling the
shutter. Spiller (1981) invented a system for thermal deposition. He used a soft x-ray re-
ectometer (a source plus a detector), placed in an evaporation chamber to register the
reectivity of successive layers. The open loop is set according to the indications of
maximum reectivity for a given layer.
It is possible by this method to obtain a multilayer with an area up to 25 cm2.
The rates of deposition vary in the range of 2100 A=s and must be carefully con-
trolled because the successive layers must be commensurate. Sometimes, especially
when multilayers of large surface are produced, a special motion of the substrate in the
evaporation chamber may be necessary to guarantee the same evaporation rate for all
points of the surface. Other diculties arise from this type of deposition: the high
vacuum required in the evaporation chamber (< 102 Pa), radiation heating of the
deposited lm, and the problems with thermal sources (alloys may segregate during
melting).
The sputter source systems (Barbee, 1981) belong to another processing method. The
glow discharge, magnetron, electron cyclotron, ion beam, and triode devices may serve as
sputter sources. The plasma discharge is always the rst step of the process. The plasma
ux is directed by the electrical potential dierence to the cathode surface, where the ions
and atoms dislodge the maternal atoms. The secondary atoms and ions establish the
proper ux (Sigmund, 1981), which passes to the substrate to deposit a layer on it. Samples
are placed on a special rotatory table, appearing at xed intervals under the secondary ux
courses. The rotation speed, precisely controlled, is the regulating factor for a designated
thickness of the layer. The purity of secondary uxes and their energies also inuence the
quality of the multilayer. The main errors in this method result from the ion and atom
inclusion into layer (there are high-energy tails in the uxes) and from heating caused by
ux energy deposition in thin layers. However, substrate rotation may overcome many of
these defects. Sputter rates range from 1 to 20 A=s; the covered surfaces may be quite
large. Today, the magnetron sputtering is the most common method, with the best results
obtained as far as the reectivity of the products is concerned.
After presenting two basic methods of layer formation, some attention must be paid
to methods of control. As mentioned earlier, reectivity estimations are of fundamental
importance in multilayer quality determination, both experimentally and in theory
(Spiller, 1981). A comparison of reectivity predicted and obtained in an experiment is
instructive, allowing, at least, understanding the source of the roughness (Henke et al.,
1986; Luck et al., 1992). Dierent peak, absolute, and integrated reectivities were mea-
sured with the use of both laboratory x-ray sources and synchrotron facilities. These re-
sults conrmed the layered structures of the synthesized materials; as a rule, reectivity
was smaller than predicted, but the results show that the optical parameters estimated
until now (Henke et al., 1982, 1988) are reasonably correct, with the shorter the wave-
length concerned, the better.
The methods just discussed only allow the deduction of an indirect image of the
multilayer structure. Other methods give direct insight into the structure. Thus, the dif-
fraction data may be very useful, but they require large sample volumes. Progress in ca-
pillary version of the diractometer (Bilderback et al., 1994), allowing the observation of
the samples as small as 56103 mm3, may bring a solution to the structural problems.
Very small samples are needed for obtaining the structural information by electron mi-
croscopy, especially in combination with a special technique of sample preparation, so-
called microcleavage (Lepetre et al., 1986). Wedge-shaped strips of materials are placed in
the electron beam in such a manner that the planes of particular layers are parallel to the
beam direction. Both the transmission image and the diraction pattern can be obtained.
The in-depth and lateral variations, the roughness, and the visual image of the structure
are in the eld of observation. High-resolution electron microscopy can give even better
results, and electron energy loss spectroscopy (EELS) may provide the complementary
chemical information on the subsequent layers (Lepetre et al., 1986).
Requirements for the application of multilayers in XRF may be summarized as
follows: They should satisfy Braggs law for the assumed wavelength domain within
permissible goniometer angles, have a high reectivity and a good spectral resolution,
suppress diraction peaks of higher order, and do not absorb soft radiation too in-
tensively. Flat or curved multilayers can be used. Dedicated designs are described in the
literature for the application of curved multilayer optics (Van Eenbergen and Volbert,
1987; Gilfrich et al., 1982). The geometric requirements imposed on the curvature of
multilayers for XRF are modest in comparison with their applications in other elds of
x-ray optics. The increasing spectral distance between K lines of the neighboring elements
when going to lower-Z elements may require a dedicated multilayer for each element.
Sometimes, great dierences in the mass attenuation coecients for the lines of neigh-
bouring elements of interest exist for a given materialattenuator. Then, one can con-
struct a multilayer eciently diracting the radiation of one element while deeply
suppressing it for other elements. The dedicated multilayers are the preferable choice for
the simultaneous WDXRF instrument, with an optimized channel for each element.
Multilayers can be also applied in a special version of WDXRF analysis, called grazing
emission x-ray analysis (de Bokx and Urbach, 1995). Curved multilayers are also used in
electron microprobes (Ovonic Synthetic Materials Co., 1987).
From what has just been described, it may be concluded that in order to analyze a
useful range of soft x-rays, at least three dierent multilayers have to be selected. Such
combinations are currently available commercially (e.g., for example from Osmic, Philips,
Siemens, Rigaku, and Shimadzu) (Ovonic Synthetic Materials Co., 1987; Van Eenbergen
and Volbert, 1987; D. K. G. de Boer, personal communication, 1998):
PX1 2d 49:3 A oxygen to magnesium
PX3 2d 195 A boron and possibly for beryllium (Nicolosi et al., 1987)
PX4 2d 122 A carbon
PX5 2d 112 A nitrogen
PX6 2d 300 A beryllium
and from the Ovonic Synthetic Materials Company (1987):
OV-040A 2d 40 A fluorine to silicon
with multilayers changing 2d spacing every 20 A up to
OV-140B 2d 140 A carbon to oxygen
and also the MoB4C structure:
OV-H series 2d 244 A beryllium to boron
up to
OV-300H 2d 300 A
Probably, materials with even greater interplanar distances can also be supplied. However,
recent scientic (except the XRF eld) interest in multilayers is centered, instead, more on
multilayers with periods of 1020 A for their excellent reectivity or for their polarizing
abilities (Schafers et al., 1998).
These materials are described in the current literature as completely thermally stable;
thus, they do not need temperature stabilization when used in x-ray spectrometers
(Nicolosi et al., 1986; Barbee, 1986; Van Eenbergen and Volbert, 1987). Some sensitivity
to the damaging inuence of intense radiation [above 0.15 J=cm2 (Kohler et al., 1985)],
conrmed later in an article by Kortright et al. (1991) and by a comprehensive report by
MacGowan et al. (1993), may limit the application of the multilayer for mono-
chromatization of dense ux of x-rays, which usually happens in synchrotron, plasma,
or laser research. Perhaps, the more important conclusion from the latter study is that,
after the impact of high power on multilayers, the amorphous carbon layer transforms
partially into a graphite form. It improves the reectivity but greatly deteriorates the
stability and changes the interplanar distances. The phenomenon of ultrafast graphitiza-
tion ( 40 ps) can, in the future, be applied for the construction of x-ray switches. These
data can be compared with the results cited in a report by Barbee (1986). He claims that
during the sputtering process of multilayer synthesis, very high temporary doses of energy
can be deposited in the layers (power density 105 W=cm3=s1), which involves a sig-
nicant increase in local temperatures (50180 C).
The relative spectral resolution of dispersive devices is often expressed in the form of
the important parameter DE=E or Dl=l, which is the basis for their choice in XRF ap-
plications. Unfortunately, this is the weakest point of the multilayer. In a commercially
available specimen, the relative spectral resolution changes from about 0.025 to over 0.1
while passing from structures with 2d 40 A to those with 2d 244 A, respectively, for
dierent measured lines (Ovonic Synthetic Materials Co., 1987), and for the structure with
2d 75 A, it changes from 0.025 to 0.04 in the wavelength range 775 A (Henke et al.,
1988), which is about three times worse (Ovonic Synthetic Materials Co., 1987) or even
more (Henke et al., 1986) than for a good classical pseudocrystal. The comparison of
spectra of the same sample by using multilayers with dierent spacings, as in Figure 23, is
very instructive (Van Eerbergen and Volbert, 1987). Relatively broad internal bandpasses
of multilayers diminish the resolution of the whole spectrographic device, seriously in-
creasing the detection limits. This is of special importance to the analysis of the L or M
series, and avoids the eorts to search the chemical shifts in x-ray spectra [although see
Habulibaz et al. (1996), where chemical shift is investigated for the SiL spectrum, dif-
fracted on a multilayer with an interplanar distance 300 A]. The relatively wide bandpass
of the multilayer can be used in a constructive way. As proven by Vrebos (personal
communication, 1997; see Fig. 24), the imminent width of the BKa peak is so great that
the contribution from the secondary beam collimation to the total width of the signal is
negligible. In that situation, the analyst can remove the ne or medium collimation or
Figure 23 Comparison of sensitivity and resolution for layered synthetic microstructures with 2d
values of 5, 12, and 16 nm from bottom to top, respectively. Increased sensitivity together with
decreased resolution on the drop in 2d is evident. (From Van Eenbergen and Volbert, 1987.)

Figure 24 Comparison of the spectra of the boron K line, obtained by a multilayer PX-3 with a
fine, medium, and coarse collimator. (Courtesy of Bruno Vrebos and Philips Analytical.)
even the collimation completely. The gain is double. It results from the greater intensity
given by the multilayer as such, as well as from the lack of the collimator, which is always
one of the most intensity-restrictive parts of the WD spectrometer. This kind of work with
a limited collimation is possible only in the region of soft x-rays, where the population of
lines is rare and in the absence of the very soft L and M lines of heavier elements.
The suppression of higher-order diraction peaks gives better spectral purity and
may at least partially compensate for the poorer resolution of multilayers. The isolation of
the weak MgKa line from the dominant CaKa line is possible by the use of PX1 structure
for the analysis of cement (Fig. 25). This is an extreme example of the superiority of
multilayers over a classical crystal in particular cases (Nicolosi et al., 1986). Another great
advantage of multilayers is their great reectivity. It should be added that the peak re-
ectivity is 310 times greater than that of corresponding classical crystals.
Multilayers were frequently used in the routine determination of light elements.
Many examples can be cited, including carbon (Nicolosi et al., 1986, 1987; Van Eenbergen
and Volbert, 1987; Philips Application Note No. 745) and boron determination (Van
Eenbergen and Volbert, 1987; Nicolosi et al., 1987; Adamson et al., 1991; Philips Appli-
cation Note No. 737 and No. 803; Uhlig and Muller, 1991; van Sprang and Bekkers,
1998), and beryllium detection (Nicolosi et al., 1987; Siemens Lab Report X-ray Analysis,
1994; Anonymous article, The Rigaku J., 1997). In the analysis, advocated by Rigaku, the
application of the high-power 4-kW generator was the additional factor, enhancing the
detection power for beryllium determination. The detection limit for that element was
found to be in the region of a few tenths of a percent. Determinations of light elements
were made using both at optics sequential spectrometers and curved optics in simulta-
neous instruments (Van Eenbergen and Volbert, 1987). After overcoming the technical
diculties, the results obtained from such analyses may seem quite trivial (Nicolosi et al.,
1987; Bonvin et al., 1995). However, not always are things going in that usual way. Van
Sprang and Bekkers, (1998) emphasized the number of problems, coupled with light-ele-
Figure 25 2W scans for Mg in cement using TlAP and PX1. (From Nicolosi et al., 1986.)
ment determination. For the analysis of boron in glass, only the combination of methods
gave good results in a whole range of the detectable concentrations: The fundamental
parameter method using the uorescent signals for the low B concentrations and the use of
the incoherently scattered radiation as a measure of the light-element fraction above 4%.
One should note some special features of x-ray spectrometry in the soft x-ray range: The
type of analysis changes from bulk to surface measurements; the inuence of the chemical
state and the subsequent wavelength shifts on the analysis can be signicant; the wave-
length of soft x-rays is comparable to the surface roughness; and the problem of the
surface quality becomes extremely important.
Considering the so-called total information depth of x-rays [see Sec.IV.G.1, Eq. (19)],
it can be calculated that in the case of iron determination in a steel sample, the eective
energy of exciting photons being 20 keV, the secondary x-rays arriving at the detector
emerge from depths up to 62 mm. A carbon signal, emitted by a coal sample excited in the
same manner, emerges from depths of only 8.3 mm. The problem looks even more dra-
matic if carbon is determined in a steel sample: In this case, signals emerge from depths as
small as 0.45 mm! This means that the analytical volume for iron is about 140 times greater
than that for carbon and the information on both constituents really refers to totally
diering volumes of the steel sample. Moreover, the method of excitation is also critical in
this case: The excitation of light elements is most ecient if made with relatively
soft x-rays, the energy of which does not substantially exceed the value of the absorption
edge. Excitation by use of hard radiation is not protable in this case, as photons are
mainly stopped inside the sample. The most restricting stage is the very short escape path
of the characteristic photons for low-Z elements.
The eect of the chemical state can be observed during the analysis of some elements
using soft x-rays. The wavelengths of La1,2 lines of chromium and manganese are 0.573
and 0.637 A, respectively, and should be analyzed in the region otherwise reserved for the
K series of oxygen and uorine, hence by the use of the PX-1, PX-4 or OV-120B pseudo-
crystals. The question is whether the limited spectral resolution of multilayers is sucient
to show such subtle eects as chemical shifts and to separate the mentioned lines of metals
from the disturbing lines of oxygen or uorine if present in the sample.
The wavelengths of characteristic x-rays in the K series are longer than atomic radii
starting from Ga (GaKa 1.337 A; atomic radius of Ga 1.26 A) and passing to the
lighter elements. Radiation with a wavelength comparable to the dimensions of an ob-
stacle always result in surface problems, with scattering and diraction at the head. One
should take into account that even the most perfectly polished sample has a surface
roughness of the order of at least one atomic radius and that the best layers in multilayer
structures have a roughness, expressed as the eective roughness se, on the order of one
to several atomic radii (Barbee, 1986; Kortright, 1996).
These latter remarks are not intended to weaken interest in multilayer optics and its
application in XRF, but only to evoke a special awareness of potential problems.
3. Spectral Resolution
Figure 26a shows the features of commonly used dispersive devise (Heinrich, 1981;
Caciuo et al., 1987; Plotnikow and Pszenicznyj, 1973; Fitzgerald and Gantzel, 1971;
Burkhalter and Campbell, 1967; Gohshi et al., 1982a, 1982b; Potts et al., 1985; Sparks,
1980; Salem and Lee, 1976; Bent, 1970; Bandas et al., 1978; Gilfrich, 1987). The width of
the bandpass DE (expressed as FWHM whenever possible) is plotted versus the energy of
radiation E; the parameter is relative to the spectral resolution DE=E. A line of given
value of DE=E is called the isoresolving line. These lines divide the whole gure into two
zones of dierent resolutions (or bandpasses). Note that both the typical dispersing
devices and typical detectors are collected in Figure 26a. Only a few detecting devices
with no resolving power (the reciprocal of the relative spectral resolution) at all exist
(e.g., Geiger-Muller counter), and no detector exists with perfect, innite resolving
power. Real dispersive devices exhibit very contrasting features, with the parameter
DE=E varying from almost 1 (scintillator counter or semiconductor photocathode) to
systems with DE=E as small as 104 [Ge (111) crystals and two- or three-crystal spec-
trometers]. Even better dispersive devices are needed, for example, for x-ray inelastic
scattering spectroscopy in which relative energy resolution near 107 is wanted. Indeed,
we can cite here some exemplary articles announcing the achievement of similar values:
1:14 107 at a level of 14:4 keV (Chumakov et al., 1996) or 2 108 for 25:7 keV
(Verbeni et al., 1996). XRF spectrometry has rather modest demands for resolution. We
see that for introducing the characteristics of the devices with spectral resolution on a
level of 108 in our diagram, the scale of Figure 26a should be prolonged by approxi-
mately four orders of magnitude at the bottom!
Another interesting conclusion can be drawn from Figure 26a. Nearly all dispersive
structures exhibit variable relative spectral resolution, but only KAP, topaz, and Ge
(111) crystals and, to some extent, also multilayer structures can be considered as iso-
resolving systems. The microcalorimeters show rather unusual behavior, compared with
other detectors. They have more or less the same absolute spectral resolution in the
whole useful range (220 keV). As we can see from the shape of the DK and DL curves,
nature does not demand isoresolving behavior from the dispersive structures. Rather,
these structures, with resolution curves parallel to the curves mentioned, would be op-
timal for spectrometric aims: The SiLi detector seems to have the better features.
Generally speaking, a bandpass range of 101103 is considered analytically useful.
Figure 26 (a) Spectral resolution of different devices: DZ spectral difference between analogous
lines of adjacent elements; DW width of spectral line; Ka1 7 Ka2 difference between Ka1 and Ka2
lines; (b) the imminent features of x-ray spectra extracted from (a) for better characterization of the
analytical demands; (c) characteristics of new microcalorimeter detectors as compared with typical
SiLi and LiF (200) dispersive structures.
Systems with bandpasses below 103 are used only in spectrophysical work. For making
a proper choice of the dispersive structure for study of chemical shifts, one has to take
into account the curves DW and Ka1 7 Ka2 (or even La1 7 La2) from Figure 26b. Figure
26b shows the spectral characteristics, extracted from Figure 26a, as a better demon-
stration of the immanent features of x-ray spectra. Depending on what matters in
analysis, the adequate choice of the resolving system should be made. The regions
occupied in the diagram by the most common [SiLi and crystal (e.g., LiF)] or most
promising (microcalorimeter) detectors are shown in Figure 26c for easier comparison
with data from Figure 26b. Figure 27 represents some example of the parallel analysis of
the same sample, based on spectra from the electron microprobe acquired by the
WDXRF system (TLAP), EDXRF system with Si(Li), and EDXRF system with the
Figure 26 Continued
microcalorimeter. For the time being, some preponderance of the LiF detector is ob-
served for light element determinations (below 4 keV) (Wollman et al., 1997), but even
this was endangered when Wollman announced the energy resolution of 2.0=0.1 eV
at 1.5 keV level (Wollman et al., 2000).
Spectral resolution is only one parameter determining the selection of a spectro-
meter. Other parameters, however, such as speed of measurement, count rate capability,
geometrical collection eciency, and ease of operation may aect the choice of the most
suitable instrument.
E. The Goniometer
The goniometer is basically a very simple construction and is the analog of a dif-
fractometer as used in x-ray diraction (the crystallographic research preceded the x-ray
uorescence method). The essential features are shown in Figure 7. The sample is posi-
tioned in front of the tube window. To account for possible heterogeneities, the sample is
Figure 26 Continued
spun about its axis at 30 rotations per minute. The analyzer crystal is positioned in the
center of the diractometer circle, rotates around an axis perpendicular to the plane of the
drawing, and passes through the macroscopic plane of the crystal. The detector moves
along the diractometer circle supported by the goniometer arm. As imposed by the Bragg
condition, the crystal rotates over an angle 2W, realizing equal angles of incidence and
diraction with respect to the crystal plane. The crystal is diracting the incident uor-
escent beam of the opening angle determined by the slit width and length of the collimator.
Rotation of crystal and detector are either mechanically coupled through gears with a
ratio of 1 : 2 or mechanically decoupled but moved by separate computer-controlled
stepping motors, but both arrangements are still implemented (cf. Tables 810 in Sec. VI).
The idea of mechanical decoupling and optical position control was rst introduced by
Applied Research Laboratories (see Sec. VI). This technique oers a number of ad-
vantages:
Alignment of crystals is no longer necessary. They can be positioned on a known
spectral line and the osets are memorized by the computer.
Figure 27 (a) NIST microcalorimeter spectrum of AlGaAs (solid line) compared to parallelly
determined EDS spectrum [with commercial Si(Li) detector]; (b) WDS spectrum of the same sample
(with TLAP applied as a crystal), spectrum transformed from wavelength into energy representation.
Observe still a little better performance of the WDS spectrometer for the considered energy region
11.6 keV. (From Wollman et al., 1997.)
The detectors can be juxtaposed on the goniometer arm and brought into position as
required by the program. Tandem arrangement of ow and scintillation is no
longer necessary.
Slewing and scanning speed range is virtually unlimited.
Optical position control (Moire fringes or optical encoder) allows very high angular
precision and accuracy.
Low-energy radiation is strongly attenuated by air. The Ka radiation of a pure
copper sample (sample 2, measured on a Philips 1410 sequential spectrometer, SWT
with chromium anode, 45 kV and 60 mA) produces 67800, 33200, and 2660 cps, respec-
tively, in vacuum and 48000, 16800, and 890 cps, respectively, in air. The results mentioned
are not easily repeated on recent computer-monitored instruments (e.g., Philips 2400)
which do not routinely allow working under air at normal pressure. To decrease the ab-
sorption of photons, all wide-range spectrometers operate in a controlled atmosphere
(vacuum or helium). The vacuum cabinet contains the entire spectrometer, except for some
instruments such as the scintillator detector. Attenuation of the high-energy radiation is
low, and to reduce the size of the vacuum chamber, the scintillation detector was and still
is placed by some producers outside the chamber. A long rectangular window of a me-
chanically strong low-density polymer (Mylar) along the diractometer circle allows the
high-energy photons to reach the detector.
High angular precision and accuracy is required for positioning the goniometer arm;
therefore, severe mechanical constraints are imposed on its construction. Typical is an
angular reproducibility of 0.001 or less and a mechanical resolution of a few thousands of
a degree or less (cf. Sec. VI). In most modern designs, 2W and W axes are decoupled.
Scanning (step size can be software selected) or measuring at preprogrammed positions
(e.g., element line, background left and right of the line for many elements) is possible.
Typical angular scan speeds (2W) are in the range from 0.1 to 180 =min and slewing speeds
can be up to 4800 =min. The slewing speed is the maximum rotation speed of the goni-
ometer arm for passing from one position to another without recording. The 2W range
covered is from 4 to 152 , with slight dierences between manufacturers. Because of the
high slewing speeds and full automation, the analysis time is severely reduced compared to
the older intsruments and, when not too many elements have to measured, is often not
prohibitively long.
Jenkins et al. (1984) and Croke and Nicolosi (1987) announced a dual-channel se-
quential spectrometer. A twin primary collimator was installed consisting of an upper, ne
collimator and a lower, coarse collimator. The beam is divided into two parts, each
striking its own crystal. Two crystals are mounted close together but with a 15 inclination
dierence. The diracted beams are detected by two detectors 30 apart. This xed angle
between both detectors, however, limits the benets of a dual-channel instrument.
Two alternative constructions should be discussed here. Simultaneous or multi-
channel instruments are equipped with monochromators set by the manufacturer (or by the
customer) at a xed position for the detection of a single element. Usually, curved crystal
optics are used, and the whole setup is optimized for that specic element with an ap-
propriate curved crystal, entrance and exit slits, and detector. The crystals are logarith-
mically or logarithmically and cylindrically curved as explained in Sec. III.D.1.e, see also
Figure 20. To give some more exibility to multichannel instruments, one or two channels
can be equipped with a scanner. The optics are either focusing (e.g., Bruker) or nonfocusing
(e.g., Philips). The at crystal arrangement is principally a reduced size of the normal
monochromator. The focusing arrangement is complicated by the fact that crystal and
detector must be moved to focus the diracted beam on the detector at any position. The
scan range of 2W for the Bruker scanner is 30 120 and 10 100 for the Philips scanner.
Full details of typical construction dierences are given in Sec. VI on instrumentation.
Two hybrid, dicult-to-classify spectrometers are discussed in this section:
MDX1000 (Oxford) and the Venus 100 (Philips). The so-called exi-channel of
MDX1000 is an energy-dispersive spectrometer. The Venus 100 has only xed channels,
but they are sequentially presented to the uorescent beam. Moreover, manufacturers are
focusing more and more on dedicated hyphenated instruments combining x-ray uores-
cence with diraction measurements, such is an ARL 8600S and Philips CubiX.
F. Detectors
The objective of a detector is the transformation of photon energy into an electrical pulse.
Pulses are counted over a period of time, and the count rate, expressed in counts per
second or any other unit of time, is a measure of the intensity of the detected x-ray beam.
From the theoretical point of view, the interaction of photons with matter is explained by
the particle character of electromagnetic radiation, not by its wave nature. Four main
classes of detectors may be distinguished for use in x-ray spectrometry according to the
medium responsible for the energy transformation: gas detectors, scintillation detectors,
semiconductor detectors, and recently introduced detectors supported on superconductive
elements (tunnel junctions and microcalorimeters). They dier in the eciency of detecting
photons of a given energy, determining the range of energy or wavelength for which they
are suited. The width of distribution of pulse amplitudes as a result of impact of photons
of the same energy determines the spectral resolution. Until recently, the best performance
in energy discrimination has been obtained with semiconductor detectors and the full
width at half-maximum (FWHM) is for the typical XRF domain in the range of 130 eV.
This allows electronic pulse-height selection discriminating the energy of the impacting
photons (at the expense of count rate, a maximum of 30 kcps). In WD spectrometers,
pulse-height discrimination is required for removal of noise of low amplitude and of
higher-order peaks of other elements interfering with the analytical line. It is a dis-
advantage typical for diraction spectrometers. High-resolution detectors are not required
in WD spectrometers because the interfering photons dier so substantially in energy that
moderate discrimination is sucient (a few hundred electron volts).
High-resolution detectors constitute the heart of energy-dispersive devices and are
discussed extensively in Chapter 3. Now, it is obvious that new types of device, super-
conductive junction detectors and microcalorimeters, exhibit energy discrimination an
order of magnitude better. Of course, in the future they might be the obvious choice in
applications demanding better spectral resolution, but the availability of the super-
conductive detectors is still a problem, as well as the maximum count rates they can
manage and their routine maintenance and price.
Only gas-lled and scintillation detectors will be discussed here as the devices sup-
plementing crystal dispersive operation. Some attention will be paid also to the micro-
calorimeter counters, because the stormy period in their development and because of the
prospects for the construction of the future generation of XRF (see Sec. VII).
1. Gas-Filled Detectors
In this type of detector, the energy-exchange process occurs between photons and gas
atoms or molecules in a strong electric eld. When a photon strikes an atom, there is a
given probability that the quantum of energy hn of the photon is imparted completely to
an orbital electron of the atom. As a result of this gain in energy, the electron emerges
from the atom with a kinetic energy of Ekin hn W (Einsteins photoelectric equation).
W is the work function of the electron for leaving its orbital and is a specic constant of
the atom. In the case of argon,
hn
Ar ! Ar e
The electron imparts its kinetic energy to other atoms, creating a series of electroncation
pairs on its path through the gas in a number equal to Ekin divided by the energy needed to
expel an electron. Values for dierent gaseous and solid detector media are included in
Table 4 Effective Ionization Potentials (eV)
He 27.8
Ne 27.4
Ar 26.4
Kr 22.8
Xe 20.8
NaI (Tl) 50
Si (Li) 3.8
Ge 3

Table 4. Subsequently, the cations and electrons are accelerated toward the cathode and
anode of the detector by the gradient of the electrical eld between both electrodes,
forming the avalanches of new ion pairs on their way to the electrodes. The discharge at
the electrodes gives rise to a current pulse in the external electrical circuit. For a range of
electrode potentials, the current pulse is proportional to the energy of the photon, and in
spectrometers, the gas-lled detectors are exclusively used in this range. This is why these
detectors are called proportional counters. Above this potential, in the GeigerMuller
plateau (Fig. 28), any photon entering the detector gives rise to a pulse of maximum
amplitude without relation to the initial photon energy. The ratio of the number of ion
pairs discharged at the electrodes to the ion pairs originally formed is called the ampli-
cation factor, generally denoted A. It is a complex exponential function of ionization
potential of the gas, anode potential, radii of detector chamber and anode wire, and the
mean free path of the electron. It implies that stability of applied potential and gas
pressure is very important for reducing statistical errors on pulse amplitude.
The basic parts of a gas-lled detector are a metal rectangular housing as cathode, a
thin wire passing through the central axis as an anode isolated from the cathode, a lling
gas, and a window either on one side or on two opposite sides of the housing. This gas
ows through or is enclosed in the housing (Fig. 29). The diameter of the anode wire
should be small. Realistic diameters are in the range of 4080 mm.
a. Flow-Proportional Counters
These detectors cover the widest wavelength range and are used in sequential spec-
trometers exclusively for long wavelength ( > 2 A) and also in simultaneous instru-
ments. The windows are made of thin foils of Mylar or polyester of 0.6, 1.5, 2 or 6 mm
or polypropylene 1, 2, or 6 mm thick. On the inner side, windows are coated with gold
or aluminum to create a homogeneous electrical eld inside the detector. Because of
these very thin windows, there is a leak of the lling gas that is compensated by a
Figure 28 Region of proportionality for gas detectors.

Figure 29 Construction of proportional counters: (a) flow counter; (b) sealed counter.
constant ow of gas through the counter (Fig. 29a). This is called a ow-proportional
counter. The gas is Ar with CH4 at a concentration of 10%, and the ow is about
0.5 dm3=h. For detectors in simultaneous instruments, helium is also used, or 88%
He 12% CO2. For very specic applications, other combinations of gases may be
useful. The gas is stabilized for pressure, ow, and temperature. This is of signicance
because a 1% change in gas pressure or temperature introduces a much more serious
67% change in pulse amplitude, which can discredit the results of the analysis (Short,
1991). The amplication factor in the proportional range is between 102 and 106. The
current pulse is conducted over a resistor by which it is converted into a voltage pulse
that is amplied, shaped, possibly discriminated in height, and counted. The count rate
is a maximum of 26106 cps. The operating voltages range from 1000 to 3000 V.
b. Sealed Proportional Detector
Basically, the construction is the same as in the ow-proportional detector but the win-
dows are thicker and no constant ow compensation for a leak is needed (Fig. 29b). The
gases used are Ne, Kr, and Xe with Al, Be, mica, Mylar, or polypropylene windows.
According to the element for which the radiation is to be detected, the most suitable
combination of crystal, gas, and windows is chosen; for example, a PET crystal with a Ne
detector with Al (for the determination of magnesium!) or a LiF (100) crystal with an Ar
or Kr detector and a Be window for the detection many of medium-Z elements. If the
lament is 80 mm thick, it is sti and easy to install, has a long lifetime, and is easily
exchanged.
Because the proportional counter is often used in tandem with a scintillation
counter, two windows are present on both sides of the main body. The absorption
probability of photons decreases with photon energy; the high-energy photons pass to the
scintillation counter through the proportional counter without being essentially absorbed.
The sealed detectors are applied in simultaneous instruments on their own and are not
used in tandem with a scintillation counter. There is no need for a tandem arrangement
because each channel is optimized for one element with the best-suited combination of
detector and crystal.
c. Pulse-Height Distribution
In the detector, a photon generates a number of ion pairs proportional to the pulse am-
plitude. The formation of ion pairs is subject to statistical uctuations, which means that
the number of pairs formed oscillates around the most probable value. A record of pulses
and their amplitudes as they emerge from the detector as a function of time is represented
in Figure 30. When these pulses are collected according to amplitude, a distribution
emerges as shown on the right side of Figure 30. The width of the distribution is measured
at half-maximum and is designated FWHM. This determines the energy resolution of the
detector. It is small for semiconductor detectors, such as Si(Li) (about 130150 eV for the
5.9-keV MnKa lines from a standard 55Fe source; see Chapter 3), about 900 eV for gas
proportional counters, and 3500 eV for a scintillation counter, all measured for the same
photon energy. Note that this distribution diers from a distribution in intensity for
a normal spectral line (intensity versus wavelength) because of natural and instrumental
line broadening.
d. Escape Peak
As mentioned in the beginning of this section, a very probable method of energy exchange
between a photon and an atom of the counter gas is the removal of an outer-shell electron.
The probability of removal of inner-shell electrons is not zero, however, and this phe-
nomenon happens in a number of interactions, in which case the specic K or L radiation
is emitted. Because the wavelength of this radiation is on the long-wavelength side of the
absorption edge, the mass attenuation coecient is low and this characteristic photon has
a good chance of escaping from the detector. The remainder of the photon energy is
transferred to the electron of which the kinetic energy is generating a number of ion pairs
but necessarily in a smaller number as an electron having received the whole photon en-
ergy. Thus, a number of pulses is created, distributed around an amplitude proportional to
the energy of this electron. The absorption edge for ArK is 3203 eV; the energy of the
FeKa line is 6403 eV. Pulses centered around 6403 7 3203 3200 eV are generated, and
Figure 30 Amplitudetime record of impulses from the detector (left) and transformation of it
into a pulse-height distribution (right).

about 3200=26 123 ion pairs are formed, 26 eV being the energy needed per creation of
electronion pair. These pulses are present in the pulse-amplitude distribution as a second
maximum on the low-energy side of the iron peak position. For Ne, Kr, or Xe, photon
energies greater than 0.87, 14.32, or 35.58 keV, respectively, are needed to excite the K
radiation. For lower energies, only L radiation is excited, resulting in an escape peak closer
to the main pulse distribution. Due to the constant distance of escape peaks in relation to
their parent uorescence peaks and high intensity in some cases, they can be used
sometimes instead of the originals.
e. Pulse-Height Discrimination
The energy resolution of a proportional counter, a few hundred electron volts at least, is
not sucient for use in energy-dispersive spectrometers (but see the simplied MiniMate
construction by Philips). The spectral line separation in wavelength-dispersive spectro-
meters is done by the crystal monochromator. As is obvious from Braggs law, however,
higher-order lines of other elements and the continuum radiation of the tube may be
present in the same spectral window (angular position) of the crystal monochromator. In
spectrometry in the ultraviolet or visible region, the higher-order diractions of the
gratings are removed by lters. This is not easily done with x-rays. For the same angle 2W,
a second-order line has a substantially dierent wavelength or energy and is far enough
apart to give two distinct pulse-amplitude distributions at the exit of the counter. For
x-rays, electronic pulse-height selection or discrimination fullls the role of lters in the
optical region. The pulse-height analysis constitutes a necessary attribute to the wave-
length-dispersive systems. Within an interval of 0.1 around 2W 37 for LiF (200) as
analyzer crystal, we nd AuLa1 in rst order, E 1:2764 keV, ThLg8 in second order
E 0:6390 keV, SnKb2 in third order, E 0:4259 keV, and LaKb2 in fourth order,
E 0:3201 keV. The energy dierence with the second-order line is 0.6374 keV and the
energy resolution of a proportional counter is about 0.3 keV. The electronic circuits of all
commercial instruments are able to discriminate between the pulses of both lines and,
consequently, also the other higher-order lines.
2. Scintillation Detectors
The energy exchange occurs in this type of detector in a medium of higher density and
with high-Z elements in the matrix, namely a thallium-doped sodium iodide [NaI(Tl)],
and as can be expected, this detector is only ecient for high-energy photons (< 2 A
or > 6 keV). The outer orbital electron for an iodide ion requires about 30 eV to be
knocked out. Hence, the originally ejected electron is imparted with almost all the
initial energy of the photon. The ejected electron dissipates its energy by promoting
valence-band electrons to an excited state 3 eV above ground level, an energy emitted
on deexcitation as a photon of 3 eV or l 410 nm. The intensity of the emitted light
pulse is proportional to the number of electrons excited by the x-ray photon
( hv=3 eV). The pulses are detected by a photomultiplier in which the light pulse
produces a few photoelectrons from the cathode material (e.g., indium antimonide).
These electrons are accelerated inside the vacuum tube between the cathode and the
rst intermediary anode, called a dynode (Fig. 31). They gain kinetic energy and
generate, in turn, a higher number of electrons from the dynode. This process is most
often repeated 10 times, resulting in a substantial multiplication of the original number
of electrons. The multiplication depends on the potential dierences between the suc-
cessive dynodes (100150 V), and the order of magnitude of this multiplication is 106,
which is called the amplication factor A. In general, the photomultiplier is a front-end
Figure 31 Layout of a scintillation counter.
tube, and the iodide crystal is in close contact with the tube window. The crystal itself
has on its outer faces a reective coating (but transparent for the photons above
6 keV) and a coating against moisture. In the external electronic circuit, the electrons
provoke a current pulse of which the amplitude is ultimately proportional to the energy
of the photon captured in the crystal. The conversion of the x-ray photons into a
current pulse occurs over dierent steps: the initial formation of a photoelectron
(I ! I0 e ), the quantied dissipation of the kinetic energy of this electron in 3-eV
steps, emission of 410-nm light photons, the production of photoelectrons from the
photocathode of the photomultiplier, and the multiplication of electrons. Although the
production of the number of light photons in the crystal (hn=3 eV) is higher than the
number of ion pairs created in a ow counter (hv=30 eV), the subsequent conversion
into electrons is inecient and roughly 1 electron is produced for every 10 light
photons! The statistical errors of each process, particularly in the photomultiplier tube,
propagate into the error of the output current pulse, thus substantially widening the
distribution of pulse amplitudes and, consequently, reducing the spectral resolution.
The DE is approximately two to three times worse than for a ow-proportional counter
(see Fig. 26a), making a scintillation counter unsuitable for ED spectrometry. However,
the resolution is still sucient for a discrimination of higher-order spectra.
Hardware for pulse amplifying, shaping, and counting are much the same as for the
proportional counters. Also, an escape peak is present, with its energy equal to the initial
photon energy minus the energy at the iodine K absorption edge.
As already discussed, in many sequential spectrometers, ow-proportional and
scintillation detectors are used in tandem, coupled in dierent ways. In another
arrangement, both detectors are shifted over 30 . A secondary collimator is placed in front
of the scintillation detector but inside the vacuum chamber; the scintillation counter
is outside the chamber, but close to the exit window. According to the manufacturer
(Rigaku), this allows a gain in count rate of 15%.
3. Alternative Congurations
Some interesting modications of the detector have been proposed in the article by Ebel
et al. (1983). These authors considered the possibility of reducing count losses between
analyzer crystal and detector (see Fig. 32) by removing the secondary collimator and al-
lowing the detector to collect a divergent beam and, at the same time, by using a position-
sensitive wire detector (with an energy resolution of 100 eV for detected photons with
energies of about 10 keV). Position-sensitive constructions are popular in many physical
applications, unfortunately not in the XRF eld. Potentially, it may lead to new solutions
for WDXRF.
Another interesting eort is the use of a scintillation gas instead of the scintillation
crystal (Kikkert, 1983; Palicarpo, 1978). This is the so-called gas-scintillation propor-
tional counter (GPSC). As is clear from Figure 26a, the resolution is substantially better
than that of its parents. The production of avalanches of ion pairs by the expelled
electrons is the same as described previously. The discharge currents at the electrodes are
not measured, however, but, rather, the scintillation pulses in the ultraviolet part of the
optical spectrum are detected by a photomultiplier as in other scintillation counters. An
essential dierence with conventional gas proportional counters is that the space charge
during the passage of a photon is avoided. The freedom-of-charge-related phenomena
enable using higher counting rates (up to 2.56104 cps; Dos Santos et al., 1993). The
lifetime of a GPSC can be quite long, up to several years, if there is no gas leakage in the
meantime. The ability to use counters with large windows positively dierentiates this
kind of construction from room-temperature solid-state detectors, such as HgI2. Their
pulse amplitude is also proportional to the energy of the incident photon. The counter
can be supplied with a digital rise-time discrimination analyzer to suppress the pulses
Figure 32 Geometry with position-sensitive detector: T x-ray tube; specimen with point P
irradiated by primary x-rays; crystal; mp mirror plane; M mirror point of P; PSD position-
sensitive detector; l distance between mirror point and detector wire. (From Ebel et al., 1983.)

forming the background (Simoes et al., 1997). This results in a much better performance
of the counter.
4. Calorimetric X-ray Detectors

Calorimetric detectors operate in extreme conditionsat temperature of liquid helium.
The essential part of the device is a low-temperature, high-Z superconducting material
with a minimal heat capacity. X-rays, even single photons, are absorbed and their energy is
transferred to phonons. The detector is thermally coupled to a cold bath. The increase in
temperature, which results from the absorption, is measured and is proportional to the
energy of the photon. The temperature is measured by a doped semiconductor thermistor,
as small as possible to minimize its heat capacity. It converts the experienced temperature
change into a change in resistance. The thermalization time of the detector is in the range
of 150 ms, and the time necessary to equalize the temperature of the detector to that of the
cooling device is 100500 ms. There is an analogy to the dead time of gas-lled and gas-
scintillation detectors. Still, there is a possibility for that type of device to allow count rates
as high as 104 cps. Now, in more modern constructions (Irvin et al., 1996), the semi-
conductor thermistor is substituted by a superconducting transition-edge sensor (TES)
thermometer. It is a strip of superconductor material biased within the transition range
from the normal to superconductive state. The greater thermal sensitivity of the device
allows the use of normal metal absorbers as a rst stage of the detector. Unlike semi-
conductors and superconductors, metals can dissipate the absorbed energy into free-
electron excitations, not phonon ones. The free-electron deexcitation process is quick and
ecient. The use of TES leads to a change in the amplier: A less noisy superconducting
quantum-interference-device current amplier is introduced. As a whole, this new com-
binations exhibits a surprising feature: The energy resolution of the detector, as measured
for the MnKa line, is better than the thermodynamic energy uctuations in the micro-
calorimeter (7.2 eV in comparison with 10.4 eV). The total spectrometer eciency
obtained up to now is reaching 80% in some low-energy regions below 5 keV and can still
be improved.
Among all the detectors mentioned in the present chapter, this one does not make
use of the ionization phenomenon. Strictly speaking, this type of detectors can measure
energy transfers even in these processes, in which no ionization takes place. It has been
recently demonstrated for, e.g., particle detection and impact energy measurements in
time-of-ight mass spectrometry of single biomolecules (Hilton et al., 1998). The quantum
eciency of such an x-ray detector can be very good ( 95%) and the absolute spectral
resolution is 7 eV in the range 0.220 keV; see Figure 26b (Silver et al., 1997). The
expected absolute spectral resolution can potentially be even better than 1 eV in the
mentioned range (Moseley, 1984). Of course, we are fully aware that this type of detector
is not intended to compete with wavelength-dispersive systems, but we must emphasize
here that the time of unbeaten behavior of crystals over all other spectral-resolving devices
has gone. It seems to be a good place to present the comparison between wavelength and
most modern energy-dispersive detectors at their present status.
5. Dead Time and Shift of Maximum Pulse Amplitude

At high count rates (from a few thousand counts per second on!), the recorded count
rate deviates proportionally from the real count rate. The reason for this discrepancy is
the slow decay of the anode charge. Cation sheaths screen the cathode. This reduces the
eective voltage between the electrodes, resulting in a lower acceleration of the electrons
and, consequently, in a smaller number of ion pairs formed. Fouling of the anode wire
by impurities in the counter gas has the same eect. This phenomenon shifts the
maximum of the pulse-amplitude distribution to pulses from apparently lower-energy
photons. Moreover, when a photon is detected, the detector is, for a short time, unable
to detect the next incident photon. This period of time is called the dead time. The
value of the dead time is about 12 ms for scintillation counters, about 0.2 ms for
proportional counters, and 200 ms for a GeigerMuller detector. To overcome this
problem, one can either choose another detector (but the choice is very limited), lower
the intensity of the exciting beam by masks or absorbers, change the geometry and the
optical arrangement (as is done in the case of synchrotron radiation), or use electronic
anticoincidence circuits or appropriate mathematical corrections. Now, after the in-
troduction of the high-power 4-kW option to the modern spectrometers, masks can be
inserted for the analysis of the major elements (e.g., in Shimadzu instruments). The
mask avoids problems with too great a count rate and its introduction is probably
easier than tube power change during the analysis.
The relation between the real and recorded count rate is
Nm
Nr 11
1 N m td
where Nr is the real count rate (count=s or cps), Nm is the measured count rate (cps), and
td is the dead time (s).
If we allow a given level of discrepancy, say a%, then the following equation is valid:
a
N r td 12
100 a
The real count rate and dead time are thus connected by a hyperbolic relation. If the
allowed value of discrepancy must be kept constant, the left-hand side of the hyperbolic
equation is constant.
However, this is only part of the problem. As already stated, a photon, arriving just
at the end of the dead time, is registered with reduced amplitude. It is only after the so-
called recovery time that a new photon is registered with normal amplitude.
An improved method for calculation of the dead time was proposed by Bonetto and
Riveros (1984). These authors used the well-known fact that the second-order peaks are
signicantly less intensive than their rst-order analogs, but the ratio of the intensities
should be constant. If it is not constant, the deviation results fully from dead-time losses in
the rst-order signal. They derived the relation
N m1
B AN m1 13
N m2
where B Nr1 =Nr2 and A Btd . The indices 1 and 2 refer to the order of the spectrum.
A summary of the constituting parts of spectrometers and the wavelength ranges in
which they are used is given in Figure 33. Note that dierent excitation sources are used in
dierent branches of XRF, namely radioisotopes for EDXRF and tubes for WDXRF;
there are also examples of synchrotron radiation. The x-ray laser is mentioned, but its
appropriate version for XRF applications does not yet exist.
Figure 33 Review of different elements serving the construction of a spectrometer: optimal range
(crossed area), feasible range (hatched area), and possible range (open area). (Adapted from Bertin,
1975.)

IV. QUALITATIVE AND QUANTITATIVE ANALYSIS
In this section, we review a number of items important to both qualitative and quantitative
analyses. The qualitative application of XRF spectrometry is obvious. In simple cases,
quite unequivocal assignments of spectral lines can be made based on a library of Ka or La
lines or, in case of doubt, when an overlap exists, Kb or other L or M lines are checked to
conrm or reject a line assignment. A few more complex situations are discussed.
Quantitative analysis may also be simple. In the low-concentration range, quasilinear
relationships are found between intensity and concentration. The same holds for de-
terminations of higher concentrations but in a very narrow range for samples with quite
comparable matrices. Interpolation on standard curves, obtained on suitable standard
samples, allows a quick and suciently accurate quantitative determination. Another
intensityconcentration relation, valid for binary samples, is based on the relative in-
tensities of Ka and Kb lines in the case that the absorption edge of another element is
located in between these two lines. In these boundary cases, matrix eects are negligible or
interbalanced but always exist. In normal practice, they compromise the conversion of
intensity into concentration in such a way that more or less complicated mathematical
methods must be used for obtaining any accurate quantitative determination. The ap-
proach by fundamental parameter programs or correction algorithms is dealt with in
Chapter 5. Between simple qualitative work and rigorous quantitative work, however, an
area of applications is situated in which knowledge of the exact concentration or the
complete qualitative composition is less important than the overall aspect of a spectrum
for recognizing classes of samples (i.e., pattern recognition). An introductory discussion of
this aspect is given in this section. Another point of interest in qualitative as well as to
quantitative work is the measurement of the background. A good estimation of the
background is necessary for obtaining net count rates, but decreasing the background
allows lowering the detection limits. The origin and magnitude of the background is
bound to the physical processes involved in the method of excitation and, thus, indirectly
to the type of spectrometer. This aspect is also treated in this section. Finally, the said
disturbing phenomena associated with the excitation of uorescence radiation, as
bremsstrahlung and the scattered radiation, can be used to increase the total analytical
information and they also have some interesting applications.
A. Background
The background in WDXRF has four main sources: (1) the coherent and incoherent
scattering of source radiation, (2) the presence of characteristic radiation of other than
sample origin (materials of sample cup masks, sample cups, collimators, spectrometer
housing, for example), (3) the detector, and (4) environmental noise (i.e., resulting from
the threshold natural radiation of materials and even from a cosmic origin). The back-
ground from characteristic radiation from construction materials of the spectrometer can
be minimized by careful construction and geometric arrangement of the device. Scattering
from sample cup masks can eciently be reduced by masks in front of the primary col-
limator. This contribution is especially great when small samples are analyzed. The beam
mask reduces the irradiated area and may totally eliminate scatter from sample cup masks.
Higher-order scatter increases with increasing wavelength. Pulse-height selection, as ex-
plained earlier, supresses counts from higher-order diraction, but this technique is most
ecient in the long-wavelength region and is decreasingly ecient toward the short-wa-
velength end. The short-wavelengths contribution to the background can be reduced by
installing adequate lters. A 100-mm titanium foil removes the characteristic lines of
chromium from a chromium anode tube, signicantly improving the conditions for the
detection of Cr, Mn, Fe, Co, and Cu (Tertian and Claisse, 1982).
For Cr tube radiation and a LiF (200) analyzer crystal, removal of scattered chro-
mium radiation may be necessary when detecting the neighboring rst-order lines. As
Table 5 shows, not very many common elements are interfering. For steel analysis, only
manganese really represents a problem. Because chromium is present in prevailing con-
centrations in the environment (tube anode!), manganese determination is also dicult
with an aluminum lter. The simplest solution in such a case is the use of a LiF (220)
crystal with better resolution in this region (but also with lower intensity). If tubes with
other targets are used, tables are similar to Table 5 but with even more complex inter-
ference if targets like Mo and Rh are applied. The other elements listed in Table 5 refer
mostly to less common elements and less intense lines. Other higher-order lines may in-
terfere as well if the concentration of elements, from which the lines are derived, is high.
For special cases, a convenient combination of tube targets, analyzer crystals, and lters
can almost always be selected. Let us look at an example for the rhodium target tube. In
the determination of palladium, PdKa1 overlaps with the Compton peak of RhKb
(Fig. 34). A molybdenum lter in the primary beam reduces this peak to a very small level,
allowing a perfect estimation of the location of the maximum and the determination of the
intensity of the palladium line.
Another ecient solution for background suppression is the use of linearly polarized
x-rays. An excellent example was given by Knochel et al. (1983) and it is reproduced in
Figure 35. The analysis of nitrogen with a small concentration of xenon was made by a
synchrotron excited XRF. Some special geometries allowing the use of polarized x-rays
have been proposed by Wobrauschek and Aiginger (1980, 1983, 1985, 1986) for the more
conventional XRF spectrometers. For EDXRF systems, a special commercial polarizing
design is available (SPECTRO A.I. Gmbh). The subject is of great signicance to syn-
chrotron-based XRF and discussed as such in Chapter 8.
A careful estimation of the background is apparently the simplest way to take the
background into account! A rst approach, but with limited application, is measurement
on blankssimple at rst glance, but the adequate blank is often a rarity. Moreover, the
blank ought to have the same scattering properties. Intensive eorts for mathematical
modeling of background were performed but frequently for other purposes.
The most common method of background evaluation is the linear (or even non-
linear) interpolation from background countings at a suitable angle above and below the
peak position (suitable means not too far away for an easy linear interpolation, outside the
tailings of the peak, and not at the position of an adjacent peak). Consequently, a good
Table 5 Interfering Lines for CrKa and CrKb with LiF 200 crystal
CrKa DE (eV) D ( 2W) CrKb DE (eV) D ( 2W)
Pm La2 10 0.05 Ho Ll < 10 0.04

La Lb2 30 0.31 Pr Lb7 20 0.24
Ba Lg5 40 0.60 Mn Ka 50 0.61
La Lb7 30 0.23 Pm Lb1 10 0.17
Ce Lb6 20 0.31 Ba Lg4 30 0.30
Pm La1 20 0.31
V Kb 10 0.56

Figure 34 Spectra of Pd excited by a Rh tube and recorded with and without a primary beam
molybdenum filter (0.1 mm Mo). The peaks are labeled PdKa, PdKb, RhKa, and RhKb with their
respective order indices. (Courtesy of ARL.)
spectral resolution of the system is essential because only in this case are peaks very
narrow and do not overlap, and the background level is easily reached in the intervals
between peaks.
Finally, we refer to a method based on the relationship of uorescent and scattered
radiation intensities versus the value of attenuation coecients. No measurements of back-
ground for the estimation of net line intensities is required in this case (Bougault et al., 1977).
If we cannot overcome the background problem, it would be advantageous to use the
background or scattered tube lines for increasing the information about the sample. There
are very interesting examples of such work and they will be shown in Sec. IV.C.
Figure 35 Synchrotron-excited spectra of gaseous nitrogen with a small amount of xenon taken in
the direction of polarization and perpendicular to the orbit plane. Counts normalized to stored
electron current are integrated over the lifetime of the detection system. DORIS was operated at
3.3 GeV and about 55 mA. (From Knochel et al., 1983. Reprinted by permission of the author and
Elsevier Science Publishers.)
B. Qualitative Spectrometry
Although the number of spectral lines is very limited compared to atomic emission
spectra in the ultraviolet or visible region, overlapping of lines in x-ray spectra does
exist. A classic example can be found in the works of Gentry et al. (1976), Sparks et al.
(1978), and Sparks (1980), and an example is reproduced in Figure 36. At energies at
which K lines of elements between palladium and cesium (about 22 and up to 30 keV)
can be present, additionally the tails of L lines of uranium and thorium are found, and
also the theoretically calculated M lines of the superheavy elements of Z 110 [in the
time which passed since 1976 this element has been discovered (Hofmann et al., 1994)]
and 126 should be expected. The erroneous attribution of some lines to these hy-
pothetical elements was the subject of extended research and long discussions (Sparks
et al., 1978; Sparks, 1980). In the software of modern spectrometers, special searching
blocks exist for the assignment of lines: The detected line is compared with data com-
piled in the program. After the initial assignment, other lines of the element are iden-
tied according to data from the library. The initial assignment is eventually rejected if
not conrmed by other lines (Fig. 37). Multichannel wavelength-dispersive instruments
are not suited for this type of work, except for elements implemented on the spectro-
meter (maximum 28 elements). Sequential instruments can cover all elements (from
beryllium on). The spectra can be displayed on the monitor screen of all modern
spectrometers, documented, memorized as les, and printed. Particular parts of the
spectrum can be scanned occasionally with higher resolution and sensitivity (step
scanning) according to the time available for the analysis and the information required.
Parts of particular interest can be displayed separately with a linear intensity axis or
rescaled to square root or logarithmic scales. The peaks can be identied on the display
by the angle 2W, by element name, either by wavelength or energy.
Figure 36 Fluorescence spectrum from a monazite particle excited with 37-keV synchrotron
radiation (ORNL DATA) shows an improved signal-to-background ratio over that excited with
5.7-MeV protons (FSU DATA). Data points every 20 eV in ORNL spectrum and every 61.8 eV in
FSU spectrum. (From Sparks, 1980.)
Figure 37 Example of qualitative analysis by rejection. The suspected MoLa peak in the lower
spectrum was rejected after comparison with the standard containing molybdenum (upper
spectrum). (Courtesy of Phillips Analytical.)

The spectrum can be scanned linearly with respect to 2W or in a more optimal way. If
Braggs and Moseleys laws are combined, the following relationship among Z, the atomic
number, and W is found:
r
m
Z s 14
k2d sin W
Z is proportional to the inverse square root of sin W. Jenkins et al. (1979) proposed
computer monitoring of the scan speed according to this equation. It optimizes the scan
speed, which represents a high gain in time especially in the low-Z range where the angular
distances between the lines are long.
The newest applications of WDXRF softwares try to avoid the old-fashioned treat-
ment of data. One such traditional manual estimation was that concerning the possible
spectral interferences. Normally, the analyst has to decide which place in a spectrum is
relatively empty of disturbing peaks and compromising background contributions. This job
was rather time-consuming, with the wide use of spectral tables and other datasets con-
cerning, for example, intensity ratios. The results were not always encouraging. Now,
virtual synthesis of wavelength-dispersive spectra is in progress (Reed and Buckley, 1996),
in the Internet demonstration version also (Buckley, 1998). The expected pure-element
spectra are loaded from the memory and installed in a region of interest of the anticipated
spectrum. Those partial spectra are apparently corrected for the expected concentrations of
the sample constituents. From the result shown on a screen of the computer, one can easily
estimate whether the region of interest is suitable for a given analysis or should be excluded.
Such a procedure makes the selection of lines for the qualitative analysis much easier, as
well as the estimation of the background and also the assessment of the detection limits.
C. Special Quantitative Applications

Although the main quantitative treatment of XRF has been left to Chapter 5, still there are
some special and nonconventional applications which proved to have potential practical
meaning. Their signicance becomes obvious when, considering the excitation process, one
wonders how great a part of the radiation is transformed into the scattered form and how it
can supplement the essential quantication based on characteristic signals.
As stated earlier, monochromatic excitation simplies the quantitative treatment of
spectral data considerably, but this case is only seldom met in WDXRF. The most
common excitation source is the x-ray tube, in which a set of characteristic lines super-
imposed on a white spectrum is generated. For this reason, only the fundamental coe-
cient method can be considered as rigorous and somewhat simplied in comparison with a
complete fundamental parameter method. How the correction terms can be derived in a
rigorous manner for the case of monochromatic excitation was shown in an article by
Kuczumow (1982). In its original formulation, the LachanceTraill equation is (Lachance
and Traill, 1966)
!
X
Wi R i 1 aij Wj 15
j6i
with aij dened as a constant written as

mjC1 E mjC2 Ei miC1 E miC2 Ei
aij 15a
miC1 E miC2 Ei

where m denotes the mass absorption coecients for primary or secondary photons of
energy E or Ei, respectively, corrected for the incident C1 and takeo C2 angles. It has
been proved (Claisse and Quintin, 1967) that this expression is valid only for boundary
conditions: monochromatic excitation and absence of enhancement. In all other condi-
tions, as are not constant, as experimentally shown (Tertian and Claisse, 1982; Lachance,
1981). It is impossible to derive a more exible algorithm with constant coecients directly
from Shiraiwa and Fujinos equation (Kuczumow, 1982; Rousseau and Claisse, 1974).
Other algorithms similar to that of Tertian (Rousseau, 1974) and Lachance COLA
(Lachance, 1981) are not recognized as fundamental. An algorithm that can be considered
partially fundamental is that of Claisse and Quintin (1967), but it suers from inaccuracies
in the approximations introduced. Later, Rousseau (1984, 1987) and Kuczumow and
Holland (1989) gave examples of algorithms derived from fundamental assumptions.
Kuczumow and Holland describe the change in a when enhancement is included
(monochromatic excitation) as follows:
!
X
Wi R i 1 aij Wij Daik Wk 16
j6i;k
where all as are dened as previously but Da is dened as
m0kC2 Ei mkC2 Ei
Daik 16a
miC1 E miC2 Ei
The new term m0kC2 Ei was introduced in Eq. (16). Although dependent on the excitation
condition E and composition, this new term has the great advantage of being dependent
on the latter in a simple way. The possibility of deriving the LachanceTraill equation
directly from the Shiraiwa and Fujino equation under the conditions applicable to Eq. (16)
is also well established (Kuczumow and Holland, 1989).
The next interesting case concerns scattered radiation as a source of analytical al-
gorithms. Similar to the derivation made by Kuczumow (1982), an expression on the basis
of coherently scattered radiation is obtained (Kuczumow, 1988):
X
Wi Rcoh
i Rcoh coh
i a ij b coh
ij Wj 17
j6i
where
mjC1 E0 mjC2 E0 miC1 E0 miC2 E0
ij
acoh 17a
miC1 E0 miC2 E0
sj E0
coh
ij
bcoh 17b
i E0
scoh
and Ricoh results from the comparison of a coherently scattered line from the sample and
from the pure element i and scoh is the mass coherent scatter coecient (for the set of
incident and takeo angles, as always in the conditions of the analysis). For Compton-
scattered radiation, analogous expressions are obtained:
X
Wi Rcom
i Rcom
i acom
ij bcom
ij Wj 18
j6i

with
mjC1 E0 mjC2 Ecom miC1 E0 miC2 Ecom

acom 18a
ij
miC1 E0 miC2 Ecom
scom
j E 0
bcom com 18b
ij
si E0
Rcom
i is the ratio of the Compton peak intensity of the sample to that of the pure ele-
ment. Equations (17) and (18) may be called LachanceTraill equations for scattered
radiation by their general appearance as well as by the way they have been derived.
These equations are less sensitive to the type of components and changes in composi-
tions than their analogs for uorescent radiation, which otherwise is an advantage in
analyses of samples widely varying in composition. From assumption, they include only
the terms for strictly dened energy values, even if the analysis is carried out with a
polychromatic source! In Table 6, the coecients a and b from Eqs. (15)(18) are col-
lected, calculated for the K lines of La and Sm, the main components of samples con-
sisting of La2O3 Sm2O3 excited by 60-keV photons at the incidence and emergence
angles equal to 80 and 70 , respectively (the example is taken from EDXRF, but it is
also instructive here).
When applied to nonhomogeneous samples, also the as are proved to be dependent
not only on the composition and the energy but also on particle size for dispersions or
layer thickness for piles of layers of dierent composition (Helsen and Vrebos, 1984a,
1984b).
Kuczumow et al. (1992) have proved that parallely with the conventional analysis of
binary AuCu alloys by uorescent lines (Fig. 38), it is possible to get similar information
using coherently or incoherently scattered tube radiation. Sometimes, the results are even
better than for the direct uorescence analysis.
Still other possibilities of using the scattered lines exist. Kuczumow et al. (1995) have
proved, by a proper mathematical transformation of the scattered Rayleigh signal, that for
light, chemically homogeneous matrices (as biological materials, e.g., wood), this new
function of scattered radiation, called the corrected scattered intensity, strictly follows the
density changes in the analyzed material (Fig. 39). The use of Rayleigh signals eliminates
the necessity of transmission measurements and brings important auxiliary information
(e.g., about the density). Although the method just described has been applied up to now
for x-ray capillary-microprobe-type measurements only, it may be used generally (Luggar
and Gilboy, 1994).
Table 6 a and b Coefcients for Fluorescent and Scattered Signals
La2O3 Sm2O3
af (La2O3 Sm2O3) 0.292 (Sm2O3 La2O3) 1.009

Daf 0.895
acoh 0.285 0.222
bcoh 1.153 0.867
acom 0.281 0.219
bcom 1.000 1.000

Figure 38 Analytical curves in the system R=W-1 versus w w0 for the CuKa line in AuCu alloys.
The solid line with open circles denotes the authors fluorescence measurements; the solid line with
crosses denotes Rayleigh measurements, and the solid line with solid square denotes Compton
measurements. R is the intensity relative to the intensity measured for the pure element and W is the
composition expressed as weight ratio; w represents the ratio of the mass attenuation coefficient of
the sample to the sine of the takeoff angle C2 . The subscript O refers to the values for the pure
element o. (Modied from Kuczumow et al., 1992.)
D. Pattern Recognition
The spectrum of a sample of complex composition is characterized by a set of lines,
documented by their position and intensity. If we imagine an n-dimensional space with the
intensities on the coordinate axes, the set of intensities determines a point in this space.
Such an intensity space is convertible into an n-dimensional space of concentrations, and
the point in the intensity representation has its equivalent in the concentration space
(Klimasara and Berry, 1987). The aim of pattern recognition is to attribute a sample to a
given class. A class is in a discrete way a set of points of similar features in the intensity or
concentration space or, in a continuous way, a subspace inside a complete n-dimensional
space. This subspace is restrained by a closed hyperplane, which can be approximated by a
number of hyperplanes of smaller dimensionality. Inherent to all experimental determi-
nations, the determination of intensity is also bound to a certain degree of uncertainty.
This implies that a point, as such, cannot be determined, only a small subspace of limited
size, limited by the assumed condence levels. Equally ill-dened for the same reasons is
the boundary hyperplane surrounding the subspace occupied by a class of samples. The
thickness of this space ring surrounding the subspace is determined in relation to each
Figure 39 Line scans from x-ray microprobe measurements that show the correspondence
between transmission (dotted) and corrected scattered (solid) data, and the sequence of tree rings of
Silesian Pinus silvestris. The linear scan was made using a 89-mm capillary and a step size of 89 mm.
(Modified from Kuczumow et al., 1995.)
coordinate axis by the appropriate multiplicity of the projection of standard deviation on

this axis.
1. Delimitation of Classes
If we consider classes as separate subspaces in n-dimensional conguration space, it is
obvious that each of these classes has its own boundary hyperplane or closed space ring.
If these hyperplanes can be determined in an analytical way, we are able to know the
boundaries of classes. In simple cases, a class can be delimited by construction of a low-
dimensional hyperplane that closely approximates the real boundary. The simplest ex-
ample is the trivial division of the whole conguration space on two categories; occupied
spaceempty space (zeroone decision). It can be done by assuming the limiting surface
(wall) inbetween the mentioned subspaces. If classes are separated by empty spaces, the
dierentiation of classes is even easier.
2. Method of Nearest Neighbours

Here, the classes are considered as small subsets of points. The classication of each new
point relies on a comparison with its nearest neighbors. Knowledge of the distance
between the sample and the nearest neighbors is essential. The accuracy of the method
depends on the way the distance is determined and the degree of complexity of the
boundaries between classes, although it can be simplied by imposing proper statistical
weights on learning samples. The method of the nearest neighbors has further implications.
Once the sample is placed in relation to the nearest neighbors, which are nothing but the
standards, a separate program can draw the average from the composition of standards,
taking the distances from the neighbors as the statistical weights for the estimation of the
inuence of each standard on the nal result (Klimasara and Berry, 1987). However, this
way of using pattern-recognition methods is the same as very conventional method of
comparison with standards! Of course, standards are no longer considered in a conven-
tional sense as some numerical values in relation to some elements, but rather as the full
patterns [compare also the genetic algorithm by Dane et al. (1996)].
3. Reduction in Number of Dimensions

All points and classes are included in the multidimensional space generated by the number
of elements present in the sample; however, some variables may be less dependent on the
related coordinates, and then the number of variables necessary to dierentiate the sample
may be reduced. The number of dimensions may also be reduced if some variables are
correlated; the most obvious way of coupling the elements is by joining them in a chemical
compound.
4. Pattern Grammar Approach

Another version of pattern recognition is also possible. The full spectra for dierent
standards and=or samples can be collected and treated as some analytical claims (sen-
tences), with peaks considered to be analogs of single words, and the whole set of spectra
as a constituent of a spectral language. At the same time, we have the complete chemical
knowledge of the same standards, with standard composition treated as the sentences,
their particular components as the single words, and such second system is the part of
another, chemical language. The task of the chemist is to translate sentences from
spectral to chemical language while working with the real samples. Even more, the
translation from one language to another can be treated as mapping (rather linear than
nonlinear!).
5. Examples
Samples may be classied into groups according to their origin. A primitive version of
such x-ray methods was demonstrated by Lagarde et al. (1984). They observed the
characteristic features of spectra of ceramics samples from western Africa and then put the
samples in order by the naked eye according to their origin. A classic reference here is
the work of Kowalski et al. (1972), which was followed by many other articles on arch-
eology. Kowalski recognized the origin of obsidian artifacts by studying a set of intensities
of 10 trace elements and projected the image of this set from 10-dimensional conguration
space into a 2-dimensional space (nonlinear mapping). Similar applications in geology are
obvious. Lo I Yin et al. (1989a, 1989b) proposed the application of the pattern-recogni-
tion-supported XRF to the initial selection and analysis of Mars Rover geological sam-
ples. They discovered on this occasion that it is not necessary to use sophisticated
detection systems. On the contrary, they applied probably the most primitive version of an
x-ray spectrometer with a proportional counter as detector. The resolving power of such a
detecting system belongs to the worst among the existing ones (compare Fig. 26a), but
even in these conditions, the results of the sample-selection procedure are good. In such
classication procedures, putting emphasis on advanced data analysis can be a substitute
for using a sophisticated high-resolution spectrometer for special analyses in dicult
conditions.
If only a limited amount of data is available, samples can only be subdivided in
groups. Discrimination of the alloys 663, B-1900, and 1455 can be done on the basis of
their zirconium content (Kevex Material Analyzer Mode 6500 brochure). Nickelcobalt
alloys were subdivided on the basis of a logical analysis of successive spectral responses: Is
the ratio contents of elements A=contents of element B greater than some assumed level
X: A=B > X (Fig. 40)? Complete analysis of the alloy was not necessary. The same is often
done when samples can be compared to standards [e.g., the framing action by software
(description of Siemens software)].
An important application of pattern recognition may be found in two-stage
analysis. For complex samples with nonlinear dependence of intensity on concentration,
the analysis can be broken down in steps with a smaller number of dimensions (lower
degree of complexity) or the samples may rst be subdivided in classes before applying
correction algorithms. The appropriate sets of dierential equations exist: they establish
the relation between the value of relative intensities [ClaisseThinh systems (Claisse and
Thinh, 1979)] or between increments of intensities [Kloyber et al. (1980) and Kuczumow
(1984) systems] and increments of concentrations. These increments are calculated with
respect to a central standard that represents the origin of a local system of coordinates. In
Figure 40 Selective procedure of the KEVEX Material Analyzer Model 6500 based on successive
analysis of the element ratios. (Courtesy of KEVEX Corp.)

this local system, a certain set of dierential equations is valid and is of linear character (if
not, it is not protable to use it in such a restricted space). After attributing the samples to
given classes, the right set of dierential equations may be used for accurate determination
of composition. The origin of the local system of coordinates may, at the same time, be the
central point of a given class.
When the delimitation of classes becomes problematical, a point in the conguration
space may be designated and a set of dierential equations, valid about this point, may be
determined. From this, the boundaries of classes can be found and determined by some
leading vectors introduced in the central points of the classes.
Yap (1987) and Yap and Tang (1984, 1985) posed the reciprocal question in relation
to pattern recognition: how to extract some number of dierentiating features from the
known classes, diering them by time and place of origin. This was used to analyze pottery
samples. Another name for this method is the training phase of the analysis.
E. Analysis on the Basis of Neural Networks

The pattern-recognition method leads us to quite dierent levels of reasoning. The most
popular recent way of working with a spectrum is to transform it numerically and show it
in two-dimensional intensitywavelength or equivalent intensity2W or intensityenergy
diagrams. Some logical artifacts result from the numerical transformation of the original
sets of signals. The interesting comparison between functioning of the electronic chip
in the binary system of information and the biological cell in the complex system of
information was presented by Cholewa during 15 ICXOM, Antwerp (Cholewa, 1998)
(see Fig. 41).
At the same time, without such a numerical presentation, a common naked-eye
observation allows one to compare a fresh spectrum to other similar pictures compiled in
our memory. Our way of reasoning is not numerical at all, but resembles some procedures
of pattern recognition. It is simply a process of attributing a sample to some class. In a
happy case, one can recall the same pattern in memory and then classify the sample as a
part of existing and well-described objects.
One of the possible ways of reasoning similar to the ways of functioning of the
human brain is by applying so-called fuzzy logic. In that type of logic, the object can
belong to the proper set with some probability, not necessary equal to 1 (belongs) or 0
(does not belong). The spectrum can be recognized in this manner, with some articial
probabilistic rules set in the very beginning of the process. An instructive example is taken
from an article by Otto et al. (1992). For the qualitative estimation of an x-ray spectrum,
the following rule is very useful: If the Ka line is supposed to be in a spectrum, then the Kb
line should be associated with it, being about 5-fold weaker.
Neural networks open another approach to the problem. They imitate the action of
neurons joined by synapses in the human brain. The articial network has a layer of input
cells and a layer of output cells. The cells from layers just mentioned are connected, some
of them directly and the majority indirectly, by the additional cells, grouped in one or
more additional, hidden layers. Each middle cell collects one or more signals from pre-
vious cells, gives those signals the proper statistical weight (e.g., according to previously
imposed rules), and sums them up. Next, the modied signal is sent from the middle cell
into one or many cells in the next hidden layer or, nally, to the output layer. The initial
information (e.g., spectrum) given to the input layer is transformed into a useful
set of information (e.g., about the chemical composition) in the output layer (Otto et al.,
1992; Larsen et al., 1992; Bishop, 1992; Bos and Weber, 1991; Luo et al., 1997). Otherwise,
Figure 41 Drawing showing the different degrees of complicacy involved in the action of (left) the
electronic chip and (right) the single biological cell, also from the informatic point of view. The
electronic chip includes only one bit of the binary information; the cell is an incomparably more
complicated system. It is a basis for the differences in computing and brain thinking. (Courtesy of
Copyright 2002Cholewa.)
Dr. Marian Marcel Dekker, Inc.
it resembles the pattern grammar method previously described. The method can be
applied for the classication of very complex spectra, for clustering the datasets, for
coupling the sets of spectra to the groups of compounds, and for nonlinear data trans-
formation between sets with dierent dimensionalities.
F. Detection Limits
The importance of the correct determination of detection limits has been acknowledged by
many chemists, especially those involved in environmental regulation. The accepted de-
nition is as follows: The limit of detection is the lowest concentration level that can be
determined to be statistically signicant from an analytical blank (Nomenclature, 1978).
The limit of detection is expressed as a concentration cL or an amount qL and is derived
from the smallest measure IL, I being the instrument reading. How the data are treated in
the statistics is described in Chapter 5. For a thorough discussion we may refer to the
article by Long and Winefordner (1983). This article also contains interesting references to
articles of Kaiser, Boumans, and others, which are therefore not repeated here. For the
derivation of some simple statistical dependencies, the small, almost forgotten book of
Beers (1958) is instructive. Finally, we can recommend the excellent discussion of the
physical origin of background sources and detection limits in PIXE and synchrotron-ex-
cited XRF given by Sparks (1980), which is also valid for WDXRF.
Here, we only invoke that according to the International Union of Pure and Applied
Chemistry (IUPAC) recommendation, the characteristic signal is statistically attributed to
the element when it is elevated not less than 3s(s standard deviation) above the back-
ground level. It makes the condence level equal to 99.86%. The detection limit is then
calculated for the standard deviation multiplicity k 3 and is expressed as a function of
intensity in a unit of time (R N=t) with t as the counting time and with the sensitivity m
expressed in cps=% or cps=ppm.
In Table 7 a series of values for cL are given for randomly chosen elements collected
from manufactures documents. No general list can be included because detection limits as
well as sensitivities depend heavily on matrix composition and on the experimental con-
ditions. Instead, this is intended as an indication of order of magnitude.
Each discussion of detection limits provides methods for deciding whether a signal
value IU for a unknown was greater than background reading IB with a given level of
condence. Another important approach is advocated and applied by Clayton et al.
(1987). They state that traditional techniques for determining detection limits have been
concerned only with providing protection against type I errors, or false positive conclu-
sions (i.e., reporting an analyte as present when it is not). They have not considered type II
errors, or false negative assertions (i.e., reporting an analyte as not present when it is).
In their article, they discuss a test of the null hypothesis c 0 versus alternatives that c > 0,
where c denotes the true but unknown concentration of an analyte in a medium and for
two models of calibration curves with known or with unknown parameters. The test is
applied to chromatographic data. Their theory can certainly be applied to XRF data, but
the attempt has not yet been reported.
G. Limits of XRF
Compared to ultraviolet (UV)visible emission spectra, x-ray spectra are oligoline ones
and very convenient with respect to the resolution of the spectrometers. The UV-visible
Table 7 Detection Limitsa
Matrix Element cL Data source
Terephthalic acid Fe 0.15 Philips

Co 0.18
Low-alloy steel C 80, 240 Philips, Siemens
Al 4, 4.5
Si 2.1, 4.1
Cr 2, 1.7
AlMg alloy Mg 7 Philips
Si 5
Ti 3
Mn 2
Cu 1
Aluminum Mg 10.5 Siemens
P 1.3
Glass powder B 1% Broll, 1985
Phosphosilicate glass B2O3 0.4% Philips
Cement Na2O 36 Siemensb
MgO 27
Al2O3 22
SiO2 50
SO3 24
P2O5 32
Copper alloys Be 0.2% Philips
Source: Data from Philips Analytical X-Ray Spectrometry Applica-
tion Notes nos. 504, 622, 623, 737, 808, 913, 916; Siemens SRS
Awendung 84=8, 86=1, 86=5, 86=6; and Broll, 1985.
a
ppm (unless otherwise specied) for 100 s counting time and k 3.
b
With use of multilayer OVO 55.
emission spectrum of iron contains some 2000 lines between 200 and 800 nm; its
complete x-ray counterpart has a dozen important lines between 1.757 A (Kb1) and
0.615 A (Lg)! For everyday work, however, only two lines, 1.936 and 1.940 A (Ka1,2)
and 1.757 A (Kb), play a role. The densely populated L series spectrum such as that of
gold has a set of about 20 lines between 0.9 and 1.5 A, a spectrum that can be
managed by a spectrometer with a relative spectral resolution of 102. The prospects
for the x-ray spectrometric range should be bright, but what are the limits to this
method?
1. Application Limits
All elements from beryllium on can be detected and=or quantitatively determined. On the
high-Z element or low-l side, the spectral resolution may be a problem for pure
spectroscopic studies, but seldom or never for qualitative or quantitative applications.
Because the emitted energy of photons is high and the attenuation coecients are low,
the critical depth is great and, consequently, the analyzed volume is very representative
of the composition of the bulk. The critical depth is the thickness dcrit of a layer parallel
to the surface, from which 99% of the intensity sensed by the detector is recruited.
It is a function of the takeo angle C2 , the linear absorption coecient mr of the matrix,
and the density:

ln 1 II1t ln102 4:61
dcrit lim ! 19
mr=sinC2
mr=sinC2 m r=sinC2
where It is the intensity emitted by a thin foil and I 1 is the intensity emitted by an in-
nitely thick sample.
For long wavelengths, mr becomes high while dcrit and analyzed volume become
low. If the sampled volume is low, the analysis may be called a near-surface determi-
nation, not representative for the bulk (see discussion in Sec. III.D.2.d). In that sense,
the results of the determination of heavy and light elements in the sample including
dierent kinds of elements can be nonequivalent. The heavier elements are then de-
termined in the bulk, whereas the light ones are determined on the surface only. This can
lead to surprising results if the process of surface segregation is occurring. Moreover,
during recent density determinations (Tsuji and Wagatsuma, 1996) of coating layers by a
similar method, Grazing emission x-ray uorescence, striking dierences have been re-
vealed between surface and bulk densities; for example, the density of a 27-nm-thick
coating lead layer was equal to hardly 35% of the normal, the bulk value of the lead
density (Tsuji et al., 1997). It is a true limit by the force of nature, although it may be
exploited for near-surface determination of light elements. From the concept of critical
depth, it is obvious that coatings can be analyzed up to certain thicknesses depending on
the absorption (and enhancement!) characteristics of the coating and substrate; the
overall thickness range is from 0.01 mm to a few hundred micrometers for the normal
angle versions of XRF.
Apart from the analysis of macrosamples, WD spectrometers may also be t to
electron microprobes, where they supplement the ED spectrometer for better spectral
resolution of light elements. Curved crystal optics is generally used because of optimum
eciency (compare the quantum eciency of a classical WD spectrometer 108, curved
crystal WD 106, and ED spectrometer 104). WD spectrometers are also needed for
heavy-particle-induced emission; because of the presence of many satellite lines, good
resolution is required (Watson et al., 1977; Chapter 12).
The dynamic range of analysis covers about ve orders of magnitude, from 103 to
100%. Below 103%, preconcentration procedures must be used.
The intensity and uniformity of exciting beams delivered by conventional end-win-
dow tubes were not sucient to allow spot analysis. However, Boehme (1987) and Nichols
et al. (1987) published the results of two-dimensional mapping executed with small beams
from high-power sources (rotating anode tubes), allowing lateral resolution of about
30 mm. This osets the boundaries to a new domain: high-spatial-resolution x-ray spec-
trometry. Still, the possibilities of the tube-excited, slit-based WDXRF microprobe are
relatively poor in comparison with an x-ray capillary-based EDXRF system or especially
proton and electron microprobes (Chapters 1113). However, for many applications, the
lateral resolution mentioned earlier is quite sucient and this technique is time-saving.
Moreover, the tube can be coupled with the polycapillary device. Note, that, for example,
the diameter of the spot obtained from the polycapillary lens is in a range 50500 mm, but
the careful work with such a beam can give a somewhat better spatial resolution. In
Sec. VI.B.3, we will discuss the milliprobes, a new solution which seems to be the most
suitable for the wavelength-dispersive mode of operation.
2. Limits of Precision and Accuracy
An analyst is always threatened by errors in the analysis outliers, random, and systematic
errors. When a given operation or measurement provokes an oset between the true and
measured values, a systematic error is said to be introduced. This oset may be due to a
wrong calibration of any kind or to a wrong standard. Such errors can only be detected by
analyzing a sample from the same batch with other techniques. Random errors and
outliers can be dealt with by statistical methods. One example of such a method is de-
scribed by Plesch (1981) and implemented in the software package Spectra 310 (Siemens).
A calibration with n standards is assumed to give a standard deviation. The standard
deviation ss is calculated according to
s
X C0 Ci 2
ss i
20
np
where Ci is the true weight fraction and C0i the result obtained; p is the number of para-
meters used in the t: p 2 for a linear and p 3 for a parabolic t. If the concentration Ca
of an element in one specimen diers considerably from C0a , the presence of an outlier is
suspected. The suspected value is eliminated, and a new standard deviation is calculated.
Ca is an outlier with a probability of P% according to the inequality (F-test) (S1=S2)2 > Fp.
The threshold values for Fp are listed in the current statistical literature. Application of the
F-test in fact checks whether a statistically signicant dierence exists between the stan-
dard deviation calculated with and without the suspected result. Possible causes of outliers
are numerous, including all kinds of human mistake, temporary instrument failure, and
heterogeneity of specimens. Recently, the numerical programs helping to segregate the
data on the true ones and outliers are available. They are based on the Grubbs test
(Grubbs, 1969; Rousseeuw and Leroy, 1987).
A measurement of uorescent radiation is, as in any other experimental determi-
nation, subject to minimal error. The standard deviation of a radiation measurement is
equal to the square rootpof the number of accumulated counts N. The real standard de-
viation is greater than N because of errors of instrumental origin. Another source of
error is the conversion of intensity into concentration and, last but not least, inherent to
the sample, microheterogeneity, which is dicult to foresee and to quantify and is present
even when all normal precautions for careful sample preparation are taken.
Heterogeneities caused by sample preparation are dealt with elsewhere. These arti-
facts should be absent here. Segregation, however, which is the origin of what we call
microheterogeneity, is a bulk (or sometimes surface) phenomenon of crystallographic
origin: solid solutions of compounds or elements that are not perfectly soluble in each
other, segregating into multiphase components. The degree of heterogeneity in the
composition of the segregated phase as well as in the size of the phases depends on the
history of the solution (thermal, chemical, or mechanical treatment). It is not easily
mastered and is dicult to quantify. Its importance for XRF analysis has been ac-
knowledged by several authors; Examples are tin and lead in solders (Glade and Post,
1970), silicates in fused beads (Novosel-Radovic et al., 1984), and silicon in SiAl alloys
(Michaelis and Kilday, 1962). The rst report we are aware of is an article by Claisse
(1957) on the determination of FeS in a sulfur matrix. A systematic study has been devoted
to this phenomenon by Helsen and Vrebos (1984a, 1984b, 1986a, 1986b) and Vrebos and
Helsen (1983, 1985a, 1985b, 1986), both by Monte Carlo simulation on hypothetical
mixtures and by measurements on samples of known segregation. It was found by si-
mulation on a (hypothetical) dispersion of spherical particles of iron in a chromium matrix
that even for a particle diameter of 1 mm, an error is introduced in the relative intensity of
FeKa of 6% (on the level of cFe 0.5) with respect to the perfectly homogeneous solution.
The eect was proved experimentally on alloys of AlSi, AlMo, and AlZn. The extent of
the eect changes with time, as in fused beads. This was demonstrated by the determi-
nations of Novosel-Radovic et al. (1984) on uxed silicates and also by Monte Carlo si-
mulations by Vrebos and Helsen (1985a, 1985b). Microsegregation imposes a true physical
limit to the accuracy obtainable by XRF spectrometry on quite a substantial number of
samples, including minerals and alloys.
3. High-Z Limit
We already insisted on the low-Z limit in Secs. III.D.1 and III.D.2, but what about the
high-energy end of the spectrum?
Commercially available generators and side-window tubes allow working at high
voltages up to 100 kV, bringing even the K line of bismuth into the potential analytical
spectrometric range. If a tungsten target is used, however, characteristic lines represent
only a minority of the integrated emitted intensity, thus, excitation is bound mostly to
continuous radiation, the maximum of which lies at 50 keV. Thus, only elements with K
absorption edges below this value can be eciently excited (Eu, Z 63, and all elements
below). The above remark is even more valid for the spectrometers with end-window
tubes, most commonly used in present-day instruments, of which the high voltage is
limited to 60 kV. Possible excitation of K lines for all the elements from the periodic table
by the tubes operating in voltages up to 160 kV is bound to metalceramic low-power
tubes, cooperating with EDXRF systems and is outside the scope of this chapter. Thus,
the available voltage limitation is the rst one.
If we return to Figure 26b and compare the spectral resolution of the LiF spectro-
meter to spectral distances between analogous lines in the K series, it is obvious that spectral
resolution is worse above 35 keV (for K lines of Pr, Z 59). This is a second limitation.
Most of goniometers have their optimal 2W range between 10 15 and 70 : At the
higher 2W end, the angular dispersion becomes insucient; at the lower 2W end, the in-
tensity becomes very low. If we choose LiF (420) with the shortest interplanar distance,
2d 1.802 A, useful measurements can be made at 10.0 corresponding to photons of
39.6 keV (Sm, Z 62 in the rst-order spectrum). This is a third limitation.
Studying Figure 26 further, we note that the spectral resolution of the LiF spec-
trometer is below the spectral resolution of the semiconductor SiLi detector for photons
of energy exceeding 17 keV, which corresponds to MoKa, Z 42. This is the fourth and
most serious limitation in the K series. For analysis in the L series, there is no such
limitation because the whole energy range lies within the capabilities of wavelength-dis-
persive devices. However, using the new microcalorimetric detectors with extraordinary
and relatively constant spectral resolution, one can anticipate the preponderance of the
spectral resolution factor for wavelength-dispersive crystals only in a region below
45 keV, which means the Ka line of V, Z 23 (see Fig. 27). Then, the ability to make the
ecient trace analysis (because of higher count rates) and the availability of the device are
still the advantageous sides of application of the crystal dispersion in the future.
The wide voltage range of generators should not be used without some awareness of
inherent drawbacks. For example, the K absorption edge of Mo is 20 keV. Thus, each
x-ray tube with characteristic lines above 20 keV and working above twice this 20 kV for
the maximum of bremsstrahlung generation is quite good for the excitation of Mo. The
potential, however, should not exceed this value substantially much because the maximum
of the white radiation would shift more and more away from the molybdenum absorption
edge and even the spectral characteristics do not improve. If we divide the mass coecient
of photoelectron excitation by the sum of mass coecients for Compton and coherent
scatters (this is a kind of measure of peak-to-background ratio), we obtain the values 76
and 18 for tube-excitation potentials of 40 and 100 kV, respectively! This is a substantial
loss in peak-to-background ratio while passing to higher voltages.
The discussion in this section shows that the advantage of high-energy photons
(generated by very high voltages in SWT) does not compensate for the drawbacks and this
probably explains why most manufacturers t EWT tubes to the instruments. During the
last years, manufacturers rather resigned from high-voltage generators and tubes, even in
high-power 4-kW constructions. The use of a higher current is now a preferred option.
Thus, we expect that only spectrometers with a high voltage up to 60 kV will dominate the
market in the future. The eective spectral range above 3040 keV should probably be left
for typical energy-dispersive detectors.
In the preceding paragraphs, we tried to show that although the spectrometers are
almost perfect, there are limits to precision and accuracy due to the nature of the sample
and to the mathematical conversion of intensity to concentration. These uncertainties are
generally greater than those introduced by instrumental parameters.
V. CHEMICAL SHIFT AND SPECIATION
The photoelectric excitation of atoms and subsequent specic deexcitation by emission of

x-rays is the basis of all qualitative and quantitative uses of XRF. The deexcitation process
was considered to take place between unique excited and ground quantum states. If these
states were always stable, x-ray emission lines were to be found at strictly determined
wavelengths or energies. However, electron density and quantum states are inuenced by
the environment of the atom with consequent wavelength shifts, or so-called chemical
shifts, of the emitted lines. Such techniques as nuclear magnetic resonance or Mossbauer
spectroscopy collect their spectroscopic information essentially from measurement of
chemical shifts. As a matter of fact, all kinds of spectral lines of electromagnetic radiation
are subject to chemical shifts. All these shifts are small and detectable only if the spectral
linewidths are suciently small and the instrument has the required spectral resolution.
For x-rays, the line shift is at most a few electron volts. An angular error DW 0.02 on the
determination of a peak position at l 1 A corresponds to 5 eV. Moreover, small tem-
perature changes of the analyzing crystal already shifts the position over similar values.
The sensitivity of peak position to the chemical environment of the atom was ob-
served at the very beginning of x-ray spectrometry by Lindh and Lundquist (1924). The
following characteristics of lines are sensitive to changes: line position (chemical shift)
(Sumbaev et al., 1968; Sumbaev, 1970; 1976), line shape (Urch and Wood, 1978), and
mutual ratios of line intensities (Asada et al., 1975). A detailed summary of the eect can
be found in the book by Agarwal (1979), for example. In spectrometers with limited
resolution, such as dierent energy-dispersive systems, most spectral shifts are hardly
detectable.
Chemical shift research has been done on high-resolution spectrometers. Gohshi
et al. (1982a, 1982b) constructed an excellent two-at-crystal instrument for studying
chemical shifts. Asada et al. (1975) and Haycock and Urch (1978) improved the use of
commercially available instruments for this purpose: by Fourier transform and iterative
procedures for peak position detection or by using ner collimators. When analyzing
crystals with large thermal expansion coecients, such as PET, are used, a temperature
variation of 1 C gives rise to peak shifts greater than the chemical shifts. Helsen and
Wijnhoven (1972) solved this problem by inserting standards at regular intervals and by
using statistical techniques for the determination of the peak position. Sumbaev and Co-
workers (1968, 1970, 1976) made experiments with an instrument in a Cauchois ar-
rangement. In an article by Kataria et al. (1986), it was proved that even using a common
solid-state SiLi detector with moderate energy resolution, it was possible to detect che-
mical eects. Similarly, Habulibaz et al. (1996) performed experiments with a multilayer
with an exact 2d spacing of 300 A, which means with poor spectral resolution. They
managed to register SiL spectra for dierent compounds, clearly showing the inuence of
the chemical environment.
Theoretically, chemical shifts can be calculated by the self-consistent eld approach
for the four quantum states involved (Manne, 1981). Unfortunately, the calculations are
largely dependent on initial assumptions, the choice of which is dicult and somewhat
random and the results are far from unequivocal. The experimental results of Sumbaev
seem to be more spectacular. He connected the chemical shift DEKL to Pauling ionicity, i,
valency m, and the parameter p, which was determined by lifetime ratios of electrons on
the levels K or L:
DEKL im pK DEK;Z:Z1 pL DEL;Z:Z1 21
He achieved an even more surprising result by presenting chemical shifts per unit ionicity
versus valence (Fig. 42). This dependence is linear and may serve as proof of both the
importance of chemical shift and the accuracy of Paulings scale. The shift can be related
to the character of the bond in the molecule or the crystal. During the formation of
a chemical bond, a rearrangement of electrons occurs, thus the formation of ions or bonds
of varying degree of ionicity, the inuence of which is reected on all electron energy
levels, sometimes more on the K level than on others levels. An example may be the shift
between the Ka position of metallic aluminum and aluminum in dierent coordination
states (IV and VI) (Helsen and Wijnhoven, 1972).
Asada and Co-workers (1973, 1975, 1976) also made measurements in which the
resulting chemical shift was attributed to the ionic bond character. They investigated the
Figure 42 Chemical shift as a function of valence. The energy shift divided by the ionicity is
plotted (solid line). The dotted curve illustrates the uncorrected values of DE. (From Sumbaev, 1970.
Reprinted with permission of J. B. Adashko.)

changes in the ratio of some spectral lines, such as those for the Kb5 and Kb1 satellite line,
and they connected them to the oxidation number of the analyte element. The results are
again surprisingly elegant (Fig. 43). Clear proof for the dependence between the shape of
lines and the oxidation number was given for manganese (Urch and Wood, 1978) and also
between the chemical shift and the coordination number for dierent elements (Gohshi,
1981). The shift of AlKa for coordination states 0, IV, and VI was given by Helsen and
Wijnhoven (1972).
The application of the determination of chemical shift to chemical speciation is
obvious. In geological samples, sulfur can be distinguished according to its dierent
oxidation states (sulfur, sulde, sulte, sulfate, and hyposulfate). Birks and Gilfrich
(1978) made measurements for sulfur using a portable low-power WDXRF instrument.
In environmental and biological samples, the oxidation state of chromium is important:
Cr(III) does not pass the cell wall, but Cr(VI) does and is suspected of being carcino-
genic. Iwatsuki and Fukasawa (1987) reported the determination of chemical states of
arsenic, selenium, and bromine. The determination of the valence of iron in welding
fumes by measuring the energy shift and the intensity ratio of Kb0 to Kb1,3 has yielded
very ne results (Fig. 44) (Tanninen et al., 1985). Kataria et al. (1986) managed to
measure the varying ratio between the total line intensities of Kb and Ka as due to
Figure 43 Satellite peak intensity ratio Kb5 =Kb1 versus oxidation number. (From Asada et al.,
1975.)

Figure 44 Relative chemical shift DE and the average valence of iron in standard samples and
four welding fumes. The squares indicate the statistical uncertainties: SS stainless steel; MS mild
steel; MMA manual metal arc technique; MIG metal inert gas technique. (From Tanninen et al.,
1985.)
dierent oxidation states of manganese using an instrument of very moderate resolving

power.
This discussion of other than elemental or quantitative information from x-ray
spectra has been intentionally restricted to x-ray spectrometry. A counterpart exists in the
spectrometry of the ejected electrons, but that discussion belongs to the domain of
spectrometry of Auger electrons or primary ejected electrons, for which higher resolutions
are available or better speciation is possible. Another and sometimes severe drawback of
these techniques is the required high vacuum and surface charging for nonconducting
specimens. It should also be mentioned that Raman spectrometry is possible in the x-ray
domain, but this eld of research is only really accessible when synchrotron radiation is
available (Sparks, 1974; Eisenberger et al., 1976a, 1976b), although performance on
conventional instruments is feasible (Suzuki et al., 1970). In analytical determinations by
synchrotron radiation, the Raman signals are often viewed as an additional disturbance
(Jaklevic et al., 1988).
Not many researchers are working in the eld of speciation by WDXRF; never-
theless, it is a eld of increasing importance, with theoretical as well as practical interest. It
gives more than simple elemental information. Moreover, the shift of lines aects the
intensity measurements for quantitative analysis, and stresses the use of the right stan-
dards for specic cases. In extreme cases, it may even be compulsory for quantitative
determinations to scan over the peak maximum for each determination and locate in each
case the intensity at the maximum for good precision and accuracy. If ultimate accuracy
should be required, correction for peak heights may be involved. The few examples given
point out that for studying the chemical shift, shape, and intensity measurements of
spectral lines, the use of dedicated instruments is indicated, although a certain amount of
useful work can be performed on commercially available instruments. A very interesting
discussion of the problems immanently connected with the analytical application of soft
x-rays can be found in the work by van Sprang and Bekkers (1998). These remarks have
the obvious implications for the speciation analysis.
VI. INSTRUMENTATION
The physical principles of a WD spectrometer do not allow dramatic dierences in the

general layout of the spectrometer. A practical instrument unites a number of construction
compromises for speed, versatility, resolution, intensity, cost, user friendliness, and other
factors, and all combinations have their own merits and their own drawbacks. Buying an
instrument is a decision that in itself is a compromise because all benets wanted by a
customer are seldom or never united within a single instrument. In this section, the main
features of the most important commercially available instruments are juxtaposed without
formulating a global or nal judgment.
A. Electrical and Electronic Features

In modern instruments, all or almost all functions are controlled by a computer. As the
electronic conguration is subject to continuous change, no details will be given here.
Mentioned here are a few aspects which were dicult to automate or, when feasible, were
hardly automated in older instruments:
High voltage generators: The costly electromechanical control of conventional
generators is replaced by computer-controlled solid-state generators, switched
or high frequency. An example of exploitation of this exible control is the
switching of the tube along the isowatt curve, modifying the high voltage but
keeping the power constant, an interesting feature if dierent intensities of the
primary x-ray beam are required for dierent elements in the analysis of a
complex sample (major, minor elements) by a sequential spectrometer.
A consequence of the mechanical decoupling of W and 2W axes lifts the necessity of
manual alignment of the crystals by giving (and memorizing) a correcting oset
angle to the W axis for each crystal. A tandem disposition for gas and
scintillation counters is no longer a necessity. The one or the other is brought
into the right position under software control.
The sin W potentiometer for continuous adjustment of the manual setting of the
lower level and window of the pulse-height discriminator is replaced by
the multichannel analyzer and electronic and electro-optical detection of the
position of the goniometer.
Automatic digital gain control corrects for pulse shrinking. Dead time is
automatically corrected. This feature ensures linear response in most
instruments to 2 Mcps for a gas-ow-proportional counter and to 1 or more
Mcps for a scintillation counter.
The main remaining electromechanical parts are the motor(s) of the goniometer in
the sequential spectrometer (dc or stepper) or alignment motors for the crystals
in the simultaneous spectrometers, the vacuum pumps, the electrovalves for gas
ow (He, N2, counter gas), cooling water and compressed air, temperature
control and fans, safety switches, sample lock and changer (internal and
external), crystal turret, collimators, diaphragms, attenuator, and primary
beam lters.
An aspect totally absent in the older instruments was remote servicing. The full
computer control allows remote servicing over a modem which substantially
reduced the mean service time, especially in situations, where the service
engineer is not close to the users facility.
B. Spectrometer Layout
Commercially available spectrometers are classied according to the x-ray tube used, the
position of the sample, sequential or simultaneous acquisition of the uorescent radiation,
hybrid forms, and some special dedicated designs. They will be discussed in the following
order:
Sequential instruments with EWT or SWT, sample down or sample up
Simultaneous instruments with sample surface up or down
Hybrid or dedicated designs
1. Sequential Spectrometers with EWTor SWT

A typical example of geometry with sample surface down (i.e., the x-ray tube positioned
under the sample) is represented in Figure 45 (layout of the Siemens-Bruker SRS-3400).
The merit of the sample-surface-down geometry is in the analysis of solutions, not easily
feasible with a sample-surface-up geometry. The positions of primary beam lters,
sample=spectrometer seal, collimator masks or diaphragms, and spectrometer optics are
clearly shown. The front end of the x-ray tube and all other parts except the scintillation
counter are enclosed in a vacuum chamber. The sample=spectrometer seal is inserted in
order to isolate the sample lock from the goniometer during sample loading. The sample
lock and goniometer are evacuated by their own vacuum pump. The aim of this parti-
cularity is the maintenance of a monochromator atmosphere of constant composition,
Figure 45 A spectrometer layout with EWT and sample-surface-down geometry. (Siemens

SRS3400. Courtesy of Bruker.)

which may contribute to the reproducibility of the determination of light elements and
prevent the contamination of the monochromator, particularly the collimator, from
contamination by powdery samples. A drawback is the x-ray absorption when light ele-
ments are to be determined. Philips recently introduced a spectrometer with the same
geometry (PW 2400 or 2404; Fig. 46) with an end-window x-ray tube, called the Super
Sharp Tube (SST). The sux super sharp points to the angle of conical nose of the tube,
allowing a decrease of the sample distance to the window. The duplex detector (replacing
the classical tandem fpc=sc construction) is a combination of a ow counter and a sealed
xenon detector (improved performance for Ka for Ti to Cu and for La to W). The scin-
tillation counter is giving an oset angle with respect to the gas counters. By this, the
scintillation counter can be enclosed in the vacuum chamber without increasing the vol-
ume of the chamber. The selection of the detector is software controlled and became
possible by the decoupling of the W and 2W axes.
Shown in Figure 47 is the method by which one or two additional xed channels can
be added. Fixed channel(s) reduce(s) the analysis time for routine analysis of samples with
one or two elements constantly present or for samples with an internal standard. ARL
Figure 46 Spectrometer with EWT and sample-surface-down position but with the addition of a fixed
channel. This channel is the similar to the ones used in simultaneous spectrometers. (Philips PW2404)
(Philips Technical Materials. Sequential X-Ray Spectrometer System PW 2404. Courtesy of Philips.)

Figure 47 Heart of the ARL 9400 spectrometer (EWT, sample surface down). Two such
monochromators, operating simultaneously, are integrated in one spectrometer, model, ARL 8420S.
(Courtesy of ARL.)
realizes the simultaneous determination of more than one element by enclosing within the
vacuum chamber a complete second monochromator of their unique extremely compact
design as represented in Figure 47. It is characterized by the complete absence of gears and
a positioning system by counting Moirefringes resulting from interference of two grating
systems.
A development of the last few years is the substitution of diaphragms by a small-
diameter aperture allowing analysis of an area as small as approximately 1 mm2 (see
Sec. VI.A.3 about milliprobes). An appropriate mechanism is moving the sample, which
allows element mapping. This feature is realized in the XRF-1700 or 1500 series of Shi-
madzu (Fig. 48). It is an instrument with sample-surface-up geometry and tted with an
attenuator, reducing the intensity by a factor of 10 (for a major element determination);
the merit of this is that no tube power switching is required for major and minor element
determination.
Figure 48 Sample-surface-up spectrometer, fitted with small-aperture collimator diaphragms and
an attenuator; all parts are enclosed in the vacuum chamber (Shimadzu XRF-1700). (Courtesy of
Shimadzu.)
Only one manufacturer still produces an instrument with SWT. A number of in-
struments of a former generation are still in use and the tubes are still available. Diano
Corporation continues the production of a spectrometer with sample-surface-up geometry
and SWT (cf. Table 10). The merits and disadvantages of EWT or SWT were previously
discussed. However, if a good homogeneity of the beam is required, a ne-focus SWT is by
far a better solution.
Sample holders of slightly dierent design for solids and liquids, for sample surface
up or down, are oered by the manufacturers. The holders for instruments with sample-
surface-up geometry are tted with a spring mechanism to press the sample against the
sample mask, both for sequential and simultaneous instruments. The holders adapting
insert for liquids have a shape that can be recognized automatically and will not be ac-
cepted if the spectrometer is not under a He atmosphere (or eventually switches auto-
matically from vacuum to He).
2. Simultaneous Instruments
All simultaneous instruments are equipped with end-window tubes with very similar con-
struction features. Up to 30 monochromators may be arranged radially around the tube
head, with alternating high and low takeo angles. One or more monochromators may be
replaced by programmable goniometers of the at (a normal at crystal goniometer of re-
duced size) or curved crystal type. The latter is small but limited in angular range; the former
has a large angular range but is large and occupies at least two positions otherwise taken by
xed monochromators. As already mentioned, Philips oers a small, low-power target
transmission tube (TTT tube) used in the spectrometer PW 1660 (Philips Technical
Materials. Simultaneous X-ray Spectrometer System PW 1660) or X0 CEM capable of si-
multaneous determination of only 14 xed elements or 12 elements when equipped with a
programmable goniometer. In most instruments the samples are placed in the surface-up
position. Some instruments (e.g., Oxford and PW2600 from Philips) irradiate in the sample-
down position. The monochromators can be tted to the outside of the vacuum cabinet, in
which case they need not be vacuum tight. Figure 49 shows a generally used geometry.
In the ARL sequential instruments, xed channels (up to eight) or a complete second
monochromator can be added. In Philips sequential spectrometer (PW 2400), an optional
two xed channels may be installed, making this instrument partly simultaneous. This is
made feasible by the use of the special x-ray front end tube, the model Super Sharp Tube.
3. Milliprobes
In an obvious eort toward the new elds of application, two companies introduced
options, which seem to be restricted up to now to the very special, laboratory-made in-
struments. Rigaku and Shimadzu independently constructed the analytical systems with
special masks: nonmovable (Rigaku) and scanning type (Shimadzu). In both versions, the
diameter of the opening is 1 mm. Coupled with a 4-kW generator and high-power tube, it
can carry out the analysis of the small pieces of a sample. In the Shimadzu version,
Figure 49 Layout of a simultaneous spectrometer with sample-surface-up geometry, typical for

Bruker MRS4000 or Philips 1606 and with the arrangement at two levels with different takeoff
angles. (Courtesy of Bruker.)

the opening is scanned before a front of the sample, thus enabling the elemental mapping
of the sample. The suggested application would be for the spot composition and density
tracing of the sample, as it has been checked elsewhere (Kuczumow et al., 1995; Luggar
and Gilboy, 1994). The construction of the milliprobe requires special attention con-
cerning the x-ray tube used. The conventional end-window tube, due to its output in-
homogeneouity, might be used only in the Rigaku arrangement, with a constant mask and
the sample moving in front of the tube. Otherwise, the relatively small output of such tubes
prevents their use as a radiation source for the milliprobes.
C. Intercomparison of Instruments
Only a limited number of manufacturers produce x-ray spectrometers. Hereafter, we will
discuss the instruments of seven manufacturers subdivided in three classes: sequential and
simultaneous instruments and a third class that we called hybrid spectrometers, because
they have characteristics belonging to both former classes. The series numbers together
with the names of the manufacturer are given in Table 8. In Tables 911, the numbers in
the top row of the third, fth, and last column refer to the manufacturer and series number
of Table 8. The reader will nd the actual addresses of the manufacturers headquarters at
the end of this subsection.
1. Sequential Instruments
In Table 9, a summary is given of the main characteristics of the current instruments as a
guide to the market for the interested reader and for those who are considering buying a
new instrument or replacing an older instrument.
a. General Remarks and Items Common to All Instruments
A question mark in the table means that the data were not available in the
brochures. When nothing is marked, it means that the given item is not
applicable.
Table 8 Available Wavelength-Dispersive Spectrometers
Sequential Simultaneous Hybrid
Manufacturer Series Table 9 Series Table 10 Series Table 11
ARL 9400 1 8600S 1

Diano 2000 2
Oxford MDX1000 1
Philips PW2400 3 PW1606 2 Venus 100
PW2404 30 PW2600 3 PW4100=20 2
X-CEM 4 PW4120=20 20
PW4110=10 3
Rigaku RIX2100 4
RIX3100 40
Siemens SRS3400 5 MRS 4000 5
Shimadzu XRF1700 6
XRF1500 60

Table 9 Presentation of Sequential Instruments
Manufacturer
1 2 3, 30 4, 40 5 6, 60
Generator
Power (kW) 3 3 3, 4 3 or 4 3 or 4 3 or 4
Voltage range=step ?60=? (opt.: ?70=?) 1560=1 2060=1 60=? 1060=1 60=?
(kV=step)
Current range=step (mA) ?100 080=0.1 10125=1 100 or 150=? 5150=1 100 or 140=?
Switch time (s) ? ? < 2,5 ? Fast
Switch mode ? ? Isowatt curve ?
Stability D%/% mains 0.0001 0.0005 0.0005 0.0005 0.0001 0.0002
Source
X-ray tube: geometry, EWT, 3 SWT EWT, 3 EWT, 3 or 4 EWT, 3 or 4
load (kW)
Anode, type, Be window Rh, 3GN, 75 Cr, EA-75, 250 Rh, SS, 75 or 125 Rh Rh, AGRh66G, Rh
thickness (mm) 75 or 125
Option other anodes W, Mo, 125 W,Pt,W=Cr, Others on request Rh=Cr,Rh,=C, Mo, W, Au, Cr Rh=Cr, Rh=W
Pt=Cr,Mo=Cr Rh=W
Primary beam filters 3 None 5 1 or 5 10 4
number
Elements Cu, Al, Fe Al, Cu Zr, Ti, Al, Cu Cu, Al Al, Ti, Ni, Cr
Sample
Sample surface Down Up Down Up Down Up
Sample turret: number 2 4 2 6 2 8 or 2
of positions
Sample=spectrometer seal y n n n y n
(yes, no)
Optics
Diaphragms: number of 3 4 6 4 5
positions
Collimators: selectable y, 4 1 y, 3 y, 2 or 3 y, 4 3
(yes, no), number

Attenuator (yes, no) n n n y n y
Crystal changer:
number of positions 9 4 or 6 8 10 8 10
Detectors: extra (yes, no) n Sealed Xe Sealed Xe, Ne, n n n
Kr
Goniometer angular range ( 2y) 17152 0146 13148 8148 4150 7148
fpc angular range ( 2y) 0115 8104 5118 4112 0118
sc and 2 axes dec c dec ? dec dec
(coupled=decoupled)
Positioning technology Moire fringe ? Optical sector ? Stepper motor Stepper motor
Continuous scanning 0.25128 0.110 0.006120 0.1240 1200 0.01180
( 2y=min)
Step scanning ( 2y=min) 0.0011.00 0.01? 0.00012 0.0050.1 0.0021
Slewing speed ( 2y=min) 4800 600 2400 1000 1000 1200
Angular accuracy ( 2y, y) 0.001 0.001 0.0025 ? 0.00001 ?
Angular reproducibility 0.0002 ? 0.0001 0.0005 0.001 0.0003
( 2y, y)
Temperature stabilization 0.1 None < 0.05 ? 0.01 0.3
( C)
Additional fixed channels y None 2 None None None
(yes, no, or number)
Parts included in vaccum All All All All except sc All except sc All
Counting electronics
Count rate (kcps): fpc 2000 ? 2000 2000 2000 2000
sc 1500 ? 1500 1000 2000 1000
Sealed 1500 4000
Duplex 3500
Pulse-shift correction Automatic Graphical display Automatic, Pulse-height Automatic Automatic
dynamic discrim.
Dead-time correction Automatic Graphical display Automatic Automatic Automatic Automatic
Computer instrument Full Partly Full Full Full Full
monitoring peripherals
Remote servicing (yes, no) y n y ? y n
Sample changer: type (x, y), xy, 1298 x, 4 or 10 xy, 6, 24168 x(?), 50, 100 xy, 8, 58, 100, ?
positions 110, 138

Table 9 Continued
Manufacturer
1 2 3, 30 4, 40 5 6, 60
Installation
Instrument dimensions: 920*1080*760 1400*860*1346 1092*1410*920 1400*1420*1054 1070*1890*880 1350*1770*1080
H*W*D (mm)
Weight (kg) 450 590 580 750 700 780
Electricity supply (V, kVA) 220, 6 208480, 10 200240, 8, 5 200220, 10 115400, 8 200220, 8 or 9
Cooling water: bar, max. > 2, 20, 0.55 > 1, 29, 19 > 3.58, 20, 611 ?, < 30, 3.511 46, , 1.5 > 1.53, 30, 310
temp. ( C), flow (L=min)
Compressed air: bar, 45, ? None 610, 20
flow (L=min)

The analyzing range of all instruments goes from Be to U and the
transuranians, except for Diano 2000, for which the range is limited to BU.
The mains power requires a stability from 10% to 10%, exceptionally from 15%
to 10%. A single phase is required, except for Rigaku, which requires three
phases.
Most commonly oered by all manufacturers are rhodium anodes for x-ray tubes.
Primary beam lters are used to remove interfering lines from the tube target element
and=or to improve signal-to-background ratio:
Al: improves peak-to-background ratio for Pb and As in light matrices;
removes RhKa line and the CrK lines
Cu: determination of Ru, Rh, Pd, Ag, and Cd; removal of interfering lines
from Rh
Fe: removes the Ka line of Rh
Ti: determination of Cr, Co, Fe, Zn; improves peak-to-background ratio
Zr: measurement of CdKa, removes the Ka line of Rh
Most manufacturers supply other lters on request.
Sample dimensions: Most instrument allow a sample size about 52 mm in diameter
(Diano: 63 mm) and about 30 mm in height (Bruker: 57 mm).
To cope with small heterogeneities, the samples are spun at 30 rpm (or 60 rpm for
Shimadzu) on most instruments (for Diano, the spinner is only available on the
sample changer with 10 positions).
The collimators are quoted in most brochures as extra-coarse, coarse, medium, ne
(high intensity to high resolution). Only Bruker mentions the divergence
angles: 0.077 , 0.15 , 0.46 , 0.93 , 1.0 , 1.90 , and 1.54 .
Crystals: All sequential spectrometers make use of at crystals.
Counters: A gas-ow-proportional counter (fpc) and a scintillation counter (sc) are
standard on all instruments, except Diano, in which the sealed Xe detector is
standard and a scintillation counter is an option. The gas ow (Ar 10%
CH4) is 12 L=min.
The electronic counters are all based on a multichannel analyzer (Shimadzu and
Rigaku probably still use a pulse-height discriminator) with an automatic pulse
shift and dead-time correction.
Available on all spectrometers is the choice of vacuum or He as the spectrometer
atmosphere, with nitrogen as option for many.
All companies supply the control unit by personal computer in more or less
sophisticated versions with software for monitoring the instrument, for
qualitative analysis, and for a number of possibilities for conversion of
intensity to concentration. All of these items are subject to change and not
discussed in detail here. The conversion algorithms are discussed in detail in
Chapter 5. The software systems supplied by Bruker, ARL, Rigaku, and
Shimadzu are all very user friendly.
Installation data are added to give the potential buyer an idea of the required space
and infrastructure. The dimensions and weight of the instruments are given
without an external sample changed t.
b. Remarks About the Individual Instruments (in Alphabetical Order as in Table 8)

ARL 9400: As far as we are aware, ARL was the rst manufacturer (and still the only
one) to use counting Moire fringes for its goniometer positioning. The
goniometer is a complete gearless construction and it has the highest slew rates
Table 10 Presentation of Simultaneous Instruments
Manufacturer
1 2 3 4 5
Generator
Power (kW) 3 3 3 0.2 3
Voltage (kV), step (kV) ?60=? ?60=? 560=1 (a) 50 2060=1
Current (mA), step (mA) ?100=? ?75=? 5125=1 4 5150=1
Stability D%/% mains 0.0001 0.0005 0.0005 0.0005 0.0001
Source
X-ray tube:
Load (kW) 3 3 3 TTT* Rh 66 G
Anodes Rh, W Rh, Cr, Mo Rh, other on Cr Rh, Mo, W,
request Au, Cr
Be windows (mm) 125, 75 125, 75 125, 75 125, 75
Primary beam filters 4 (a) 10 3
positions
Elements Cu, Al, Fe
Primary beam attenuators y, 14 y
(Yes, No)
Samples
Sample surface Up Up Down (b)
Size: diameter, height (mm) 75, 50 51, 40 51, 40 40, ? 52, 57
Sample changer (positions) 11, 32, or 8 (b) 6, 72, 300 8, 58, 100, 138
Monochromator (fixed
channels)
Takeoff angle ( ) ? 29, 44 29, 44 25, 39, 5 26, 24 (a)
Maximum number 30, 20, 11 (c) 28 (a) 28 14 28
Crystals Curved x Log. curved
Detectors Gas counter, sc Gas (Ar flow, Ne, fc, sc
Kr sealed)
Element range BeU BeU BeU
Goniometer

Maximum number 1 (d) (a) 2 (c) 2 (d) 8 2 (a)
Collimators 3 1 Slits
Crystals number 9 1 (LiF 200, 4 (PE, InSb, Ge, Up to 4
220, Ge) LiF 200, 220)
Type Flat Flat Cyl. curved
Scan speed ( 2y=min) 0.25128 0.0676 0.0676 0.0676
Step scan ( 2y=step) 0.0011 0.01 0.01 0.01
Slewing speed ( y=min) 4800 1000 480 480
Angular accuracy ( 2y) (LiF) 0.015 ? ? ?
Angular resolution ( 2y) 0.001 ? ? ?
Angular reproducibility ( ) 0.0002 0.003 < 0.01 < 0.005
Angular range gas counter 17155 5120 10100 8547
( 2y)
sc ( 2y) 0115 5120
Detector sc, Kr-sealed fpc
Element range BU BU FU
Spectrometer environment Vac Vac, He, air Vac, other on Vac, other on Vac, air
request request
XRD channel (yes, no) y n
Installation
Dimensions: 1350*1400*950 1804*1232*877 1190*815*1230 1800*1810*950
H*W*D (mm)
Weight (kg) 1000 900 580 900
Water supply(bar, max. > 3, < 18, 5 3058, < 20, 38, 20, 3

C, L=min) 610
Compressed air (bar, L=min) ? 45, ? 610, 20

Table 11 Hybrid Instruments
Manufacturer
1 2, 20 3
Generator
Voltage (kV)=current 4050=4=200 50=4=200 id.
(mA)=power (W)
Stability D%=%mains 0.007 0.0005 id.
Max. mains 210250 180264 id.
variation (V)
X-ray source
Tube Similar (a) Target transmission id.
Anode Rh Sc Cr
External Cooling None None id.
Sample
Sample surface up, down Down Down id.
Spinning (rpm) 30
Dimension (diameter, 48, 40 2647, 40 id.
height in mm)
Sample changer ? Single, 10 Single
Spectrometer chamber Vac, He optional Vac, He Vac
Monochromator (fixed)
Element covered FU S, S-bg., Zr, Ni, Al, Si, Na, Mg,
Ni-bg., Mn, Ti, Mn, K, Ca,
Mn-bg., V, V-bg P, S, Fe
Crystals Flat, curved optional Curved id.
Additional Flexi-channel None id.
spectrometers (EDXRF)
Dimensions 1090*800*800 id. 1200*750*960
(H*W*D in mm)
Weight (kg) 160 id. 180
of all spectrometers. In the series 9420S, two goniometers or additional xed

channels can be tted, adaptable to a great variety of analytical situations,
excellent for rapid nonroutine industrial control, reducing the analysis time by a
factor of 2 with respect to a conventional sequential spectrometer. Separate
vacuum pumps support the vacuum for the sample lock and the monochromator.
Diano 2000: This oers dual-target tubes. The targets are push-button selected and
no moving parts are present (dual lament). Two collimators are oered: a
0.032-in. spacing beam tunnel or a 0.010-in.-spacing diracted beam soller
slit. The instrument is not temperature stabilized because the 45-kg bronze
bull gear goniometer has a suciently high thermal capacity, avoiding rapid
temperature changes. It is, however, not sucient when one wants to measure
peak shifts. The crystal in the turret must be individually tuned. The W and 2W
axes are coupled but with a bisector arrangement and moved by a dc motor.
The standard detectors are a ow-proportional counter and sealed Xe, the
scintillation counter is an option. The counting is also by a pulse-height
selector. Diano oers a xed-sample and xed-element mode for analysis.
Philips PW 2400, 2404: Both types dier only in the power output of the generator.
The tube power is switched along the isowatt curve (i.e., by keeping the power
constant when either the voltage or current is changed). The xed channels
that can be added have as the detector either a ow-proportional counter
(3000 kcps), Xe-sealed (1000 kcps), Kr-sealed (2000 kcps), Ne-sealed
(2000 kcps) proportional counters, or a scintillation counter (1500 kcps). The
positioning of the goniometer is done by optical disk, a sophisticated high-
performance system, giving the highest angular accuracy and reproducibility.
The goniometer is driven by dc motors. The external sample changer accepts
samples of nonuniform size.
Rigaku 2100, 3100: Both types dier only in power output of 3 and 4 kW. The
collimators are either standard=high resolution or standard high resolu-
tion=ultralight elements. The attenuator in front of the monochromator crystal
reduces the intensity by a factor 10. The advantage should be that it avoids
power switching of the x-ray tube. The sample-surface-up geometry makes it
dicult, if not impossible, to analyze solutions. A diaphragm of 1 mm
diameter allows small-spot analysis. A built-in cleaning system removes the
impurities of the wire in seconds in this instrument because the ow-counter
eciency deteriorates by contamination of the wire electrode.
Siemens (Bruker) SRS 3400: The instrument is rather conventional and easy to
service. The positioning of the decoupled arms of the goniometer is done by
stepper motors. The positioning of the sample holders is very reproducible. The
external sample changer accepts nonuniform samples also. An excellent
software SPECTRA PLUS is supplied for qualitative, semiquantitative, and
quantitative analyses. The instrument was formerly sold under the name of
Siemens but is taken over by Bruker Analytical X-Ray Systems (Bruker AXS).
Shimadzu XRF 1700, 1500: The dierence between both instruments is that the
selection of lters, diaphragms, attenuator, and crystals is automated in the
1700 model. A special feature of this instrument is the presence of diaphragms
of diameter 1, 3, 10, 20, and 30 mm. The 1-mm diaphragm together with an
appropriate sample positioning system allows element mapping.
2. Simultaneous Instruments with Sample Surface Up or Sample Surface Down

A summary of the characteristics of the instruments capable to determine simultaneously a
number of the elements is given in Table 10. The instruments are composed by a few till
maximum 30 small-size high-eciency spectrometers as discussed earlier, optimized for
one particular element. The set of spectrometers is dedicated to a particular series of
samples as used in, for example, the cement or steel industry. To attribute some exibility
to these instruments, one or more scanning goniometers are added.
a. Remarks and Features Common to All Instruments
All manufacturers use x-ray tubes with either a 75- or 125-mm-thick Be window.
The detectors oered are ow-proportional gas counter (Ar), sealed gas counters
lled with Kr, Ne, or Xe, and a scintillation counter.
The linearity of the photon count rate is equal or similar to the one given for
sequential instruments.
Temperature stabilization is either individual for each spectrometer or for the
ensemble.
Electricity power supply is single phase, 1015 kVA.
ARL oers the possibility of adding an additional x-ray diraction device within the
uorescence spectrometer.
Other manufacturers oer integrated sample transport from the spectrometer to an
x-ray diraction instrument. The CubiX XRF from Philips is a simultaneous
spectrometer for up to 14 elements, similar to the XCem. It is integrated in the
same module with an x-ray diraction instrument; both can be juxtaposed,
allowing a rapid sample transport from one instrument to another. Both devices
are operated by a single personal computer. Cubix represents a modular concept
for integrated analysis, including elemental and crystallographic determination.
b. Remarks About the Individual Instruments (in Alphabetical Order as in Table 8)
APR 8600S
1. The primary beam lter takes the place of three monochromators and cannot be
t alongside an XRD channel.
2. Eight positions for cassettes for large samples (75 mm and height of 50 mm);
11 and 32 positions for small samples (52 mm and height of 30 mm).
3. Thirty monochromators can be tted or 20 plus 1 goniometer, or 11 plus an
XRD channel.
4. The goniometer is the same as the module of the sequential instrument.
Philips PW1600: Maximum two xed channels can be substituted by a program-
mable goniometer (with at crystals and parallel beam collimation). One
programmable channel occupies space as for one xed channel.
Philips PW2600
1. Switching time of the generator is 2 s and the tube is switched along the
isowatt curve.
2. Particular feature of this instrument is that it allows liquid samples to be handled
also.
3. Two dierent goniometers can be tted: (1) one with a at crystal and parallel
beam collimation and it takes the space of one xed channel; (2) one with a
cylindrically curved crystal (logarithmic spiral optics) and two slits and it takes
the space of three xed channels. Optional beam attenuators can be tted,
enabling all channels to handle concentrations from ppm levels up to 100%.
Philips X9 Cem: The x-ray tube is a low-power Target Transmission Tube (TTT),
(Sec. IIIA). Because of the low power (200W), this instrument does not need
external water cooling.
Siemens MRS 4000: High power (4 kW) and high speed instrument.
3. Hybrid Instruments
The instrument from Oxford MDX1000 is classied as hybrid because it combines a WD xed
channel with what is called a Flexi channel, an EDXRF unit. The x-ray tube is similar to the
target transmission tube, produced by Philips, but no other details are given in their brochures.
The instrument series Venus 100 from Philips are called hybrid because Philips uses
xed channels, which are, however, switched sequentially in front of the sample. The in-
struments are delivered for specic purposes: The PW4110=10 is provided for the analysis
of industrial minerals, particularly for the ceramic industry, and the PW4100=20 and
PW4120=20 for the determination of, for example, nickel, sulfur, and vanadium in pet-
roleum products. The element range can be adapted to specic purposes.
Both instruments from Oxford and Philips are simple, low-cost, but high-perfor-
mance devices which can be used in harsh industrial environments; they are simple to
install and are characterized by small dimensions, light weight, no water cooling, no
compressed air, and no severe requirements for the stability of the mains.
Hybrid instruments are presented in Table 11.
4. Instruments Dedicated to Special Applications and Supplements

Two manufacturers, Siemens and Philips, supply for the semiconductor industry trans-
formed versions of their sequential spectrometers SRS 3300 (power up to 4 kW, mapping
possible) and PW 2800, respectively. The main feature is the sample area which must
accept silicon disks as large as 10 in. in diameter. The sample introduction system is au-
tomated and meets the standards for working in a cleanroom environment.
The manufacturers also provides as many auxiliary devices as possible. Advanced
analysis lines are available from Rigaku, Philips, and Siemens, which oer a complete
set of the mills, uxers, and polishing devices for the XRF and XRD laboratory.
Worth noting is that, on the other hand, during the last years, some new companies
appeared on the market, oering not whole instruments as such but only some specialized
parts of instrumentation. Among the most important participants in this kind of activity,
the following should be mentioned:
Advance Hivolt, oering x-ray generators, especially with 4 kW power
X-Ray Optical Systems Inc., supplying x-ray focusing and collimating polycapillary
optical devices plus designing the optical systems with x-ray semilens
Osmic Inc., the main producer of multilayers
Corporation Scientique Claisse Inc., producing uxers for sample preparation
Contact with these producers can be very meaningful alternative in case of constructing
new, home-made, and dedicated version of an instrument.
We conclude this subsection on the intercomparison of instruments with a list of the
addresses of the headquarters of the manufacturers:
ARL Applied Research Laboratories S.A., En Vallaire Ouest C, case postale, CH-
1024 Ecublens, Switzerland
Diano Corporation, 271 Salem Street, Woburn, MA 01801, USA
Oxford Instruments, 19=20 Nueld Way, Abingdon, Oxon OX14 1 TX, England
Philips Analytical X-Ray BV, Lelyweg 1, 7602 EA Almelo, The Netherlands
Rigaku International Corporation, 3-9-12, Matsubara-cho, Akishima-shi, Tokyo
196, Japan
Shimadzu Corporation, International Marketing Division, 3, Kanda-Nishikicho
1-chome, Chiyoda-ku, Tokyo 101, Japan
Siemens, A.G., now: Bruker AXS GMBH, Oestliche Rheinbrueckenstr. 50, D-76187,
Karlsruhe, Germany
VII. FUTURE PROSPECTS
The time passed since the rst edition of this handbook has been one of the most stormy
periods in research and applications of x-rays since their discovery! It is well known how
much Rontgen was confused, although totally convinced, by the impossibility to de-
monstrate the electromagnetic nature of x-rays through reection, diraction, or inter-
ference experiments! For many years, it remained impossible and further progress was very
slow and tedious. Recent years have brought the real breakthrough. We know of three
recent realizations of x-ray lenses:
Two diractive:
1. Zone plates (in other words, Fresnel diracting structures), earlier restricted to
the very soft x-rays. They are very important for the construction of the x-ray
microscopes and for the observation of living biological objects in the so-called
water window. But now, by combining the Fresnel diraction patterns with
Braggs phenomenon, the special BraggFresnel lens was constructed, well
suited for focusing hard synchrotron radiation (Aristov et al., 1986; Snigirev,
1995; Snigirev et al., 1995; Chevallier and Dhez, 1997).
2. Snigirev refractive lens (Snigirev et al., 1996; 1998; Elleaume, 1998; Hastings,
1996; Eskildsen, et al., 1998), consisting of one or two mutually perpendicular
arrays of holes drilled in low-Z dense material (Be, Al). Depending on the
number and shape of the holes, they can focus hard x-ray beams,
One version using total reection:
1. Kumakhov polycapillary lenslike device, which might be somewhat poor in
focusing capability (spot is 50500 mm wide) but very ecient with respect to
the fraction of the primary input power turned into a small spot on the analyzed
surface. Interesting products were announced by X-Ray Optical Systems Inc.,
Advertising Materials.
In parallel, great progress was realized in the construction of energy-dispersive de-
tectors with increasingly better spectral resolution. The most promising device seems to be
the microcalorimeter detector, a device with very good spectral resolution parameters.
Moreover, its spectral resolution is more or less constant over the whole spectral range
covered (120 keV). With such a device, the spectrum deconvolution problems, so char-
acteristic for devices with poor spectral resolution, should vanish. Potentially, it lowers the
detection limits, by narrowing the energy region in which the very sharp peak is placed.
Only a very restricted number of background counts is detected in that region, thus im-
proving the peak-to-background count rate ratio. However, the detection limit depends on
the maximum count rate allowed for these detectors, which is, at the moment, very re-
stricted. Recent discussions show (Ladbury, 1998) that intensive work is going on to
overcome this shortcoming in the nearest future. The aim is to get the device with an area
of 40 mm2, with count rates up to 105 cps.
Another progress took place in the construction of time-resolved excitation sources.
The classic radiation generator for the purpose is synchrotron. Probably much more
convenient, the portable and switchable version of a time-resolved x-ray source will be a
compact-ash source. Furthermore, the construction of the x-ray laseran old dream!is
also progressing, maybe slowly, but in a promising direction.
Collected together, all available information about this progress justies hope on the
construction of new versions of existing instruments as well as the advent of new ones. It is
worth noting that in the present chapter we considered an XRF spectrometer mainly as a
device used for the determination of elemental composition. What is now discussed tes-
ties that future instruments will give both compositional and spatial resolution (mi-
croprobe) and time resolution (kinetic probe). New kinds of lenses and normal incidence
mirrors give an impetus to the construction of x-ray microscopes also in the hard part of
the x-ray spectrum. One can easily imagine a microscope (but one easily construct!)
working in the hard x-rays regime supported by two dierent x-ray lensesone acting as
an ocular lens and one as an objective lens.
The new version of the microprobe could then eciently concentrate x-rays (e.g., by
Kumakhov polycapillary) on the conned areas and then record the uorescent radiation
with the excellent spectral resolution of a microcalorimeter as the energy-dispersive de-
tector with the whole spectrum completed in one operation. Such a device is now under
construction in the National Institute of Standards and Technology (Wollman et al.,
1997a, 1997b; Anonymous, 1997). The microcalorimeter detector, attached to a scanning
electron microscope, has, for the time being, a spectral resolution of 7.2 eV 0.4 eV,
calculated in the standard way for the MnKa line, or 2.0 eV for 1.5 keV (Wollman et al.,
2000). Count rates are below 150 cps, but it is, by far, not the last word in this matter.
A newcomer in the generation of possible applications of the classical WDXRF,
rather unexpectedly brought to the awareness of scientists, was that the extended ne
structure of uorescent spectra emitted by solid samples can be observed (Hayashi et al.,
1997; Kawai et al., 1998). Up to now, this eld was reserved for the absorption mode,
mostly in combination with synchrotron radiation. The discovery of the extended ne
structure in experiments performed under normal laboratory conditions opens a new eld
in the study of local structure in condensed matter and makes this method available to
lower-budget laboratories.
ACKNOWLEDGMENTS
All manufacturers of instruments are gratefully acknowledged for supplying documents

about their instruments. Mr. P. Van der Aa, Dr. B. Volbert, and Dr. ir. B. A. R. Vrebos
from Philips Analytical and Mr. S. Ornigg, Dr. K. E. Mauser, and Dr. N. Broll from
Siemens (Bruker) AG deserve our gratitude for invaluable advice and critical reading of
the manuscript. Dr. D. de Boer is acknowledged for supplying us with his knowledge on
the most recent progress in multilayer research. A. Kuczumow thanks the Catholic Uni-
versity of Leuven for a fellowship that enabled him to participate in the rst edition of this
work and the Flemish Government for a fellowship helpful in the present revised version.
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DK1838 - ch02 Chapter 2 (Two) Handbook of X Ray Spectrometry

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2

Wavelength-Dispersive X-ray Fluorescence

Copyright 2002 Marcel Dekker, Inc.

Copyright 2002 Marcel Dekker, Inc.

Figure 2 Representation of Moseleys law of K and L spectral lines.

Copyright 2002 Marcel Dekker, Inc.

II. FUNDAMENTALS OF WAVELENGTH DISPERSION

The crystal monochromator is the heart of a wavelength-dispersive spectrometer. Wave-

Figure 4 Derivation of the Braggs law. ABC is the path difference.

Copyright 2002 Marcel Dekker, Inc.

wavelengths belonging to dierent spectral orders, a pulse-amplitude selector or detector is

1251.56 1254.19 42 Mo KMIV KbII5 2

The dierences between wavelength-dispersive (WD) and energy-dispersive (ED)

III. LAYOUT OF A SPECTROMETER

Figure 7 A wavelength-dispersive spectrometer: FC proportional flow counter; SD scintilla-

Copyright 2002 Marcel Dekker, Inc.

Freedom from interfering lines is important. The scattered characteristic lines of

Figure 12 X-ray tube with stepwise configuration of the anode.

5. Tubes with Rotating Anode

Copyright 2002 Marcel Dekker, Inc.

According to our knowledge, three companies, Rigaku, Siemens, and Enraf-Nonius,

6. Compact Flash X-Ray Sources

Figure 15 Principle of switched power supply: dc=dc convertor.

Copyright 2002 Marcel Dekker, Inc.

B. X-ray Tube Spectrum

C. Collimators and Masks

Copyright 2002 Marcel Dekker, Inc.

Table 2 LiF: d Spacings for Different Orientations and Angular

Crystal 2d (A) Dispersion

LiF (422) 1.652

Note: Calculated for W angles corresponding to MnKa (2.102 A) and n 1.

Copyright 2002 Marcel Dekker, Inc.

Crystal 2d (nm) Element range Remarks

LiF(420) 0.180 NiU High resolution, special applications for

Copyright 2002 Marcel Dekker, Inc.

Figure 20 Focusing of x-rays by a logarithmically curved crystal. (Courtesy of Siemens AG.)

that of conventional at geometry). The curved crystal geometry is applied in simultaneous

Copyright 2002 Marcel Dekker, Inc.

c. Reectivity and Thickness of a Multilayer

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Table 4 Effective Ionization Potentials (eV)

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Figure 28 Region of proportionality for gas detectors.

Copyright 2002 Marcel Dekker, Inc.

Copyright 2002 Marcel Dekker, Inc.

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4. Calorimetric X-ray Detectors

5. Dead Time and Shift of Maximum Pulse Amplitude

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CrKa DE (eV) D ( 2W) CrKb DE (eV) D ( 2W)

Pm La2 10 0.05 Ho Ll < 10 0.04

Copyright 2002 Marcel Dekker, Inc.

Copyright 2002 Marcel Dekker, Inc.

C. Special Quantitative Applications

with aij dened as a constant written as

Copyright 2002 Marcel Dekker, Inc.

where all as are dened as previously but Da is dened as

Copyright 2002 Marcel Dekker, Inc.

mjC1 E0 mjC2 Ecom miC1 E0 miC2 Ecom

Table 6 a and b Coefcients for Fluorescent and Scattered Signals

af (La2O3 Sm2O3) 0.292 (Sm2O3 La2O3) 1.009

Copyright 2002 Marcel Dekker, Inc.

coordinate axis by the appropriate multiplicity of the projection of standard deviation on